orgsyn.org
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132.148.79.46
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URL:
https://orgsyn.org/demo.aspx?prep=v88p0353
Submission: On April 26 via api from US — Scanned from DE
Submission: On April 26 via api from US — Scanned from DE
Form analysis 1 forms found in the DOM
Name: aspnetForm — POST ./demo.aspx?prep=v88p0353
<form name="aspnetForm" method="post" action="./demo.aspx?prep=v88p0353" onsubmit="javascript:return WebForm_OnSubmit();" id="aspnetForm">
<div>
<input type="hidden" name="__EVENTTARGET" id="__EVENTTARGET" value="">
<input type="hidden" name="__EVENTARGUMENT" id="__EVENTARGUMENT" value="">
<input type="hidden" name="__LASTFOCUS" id="__LASTFOCUS" value="">
<input type="hidden" name="__VIEWSTATE" id="__VIEWSTATE"
value="/wEPDwUKLTU1MTkwODgwNw9kFgJmD2QWAgIDD2QWBgIBD2QWAmYPZBYCAgEPEGRkFgFmZAICD2QWAmYPZBYCAgMPEGRkFgBkAgcPZBYCZg9kFgICAQ9kFgICAQ9kFgJmDxYCHglpbm5lcmh0bWwFnKwCPGEgaWQ9InRvcCIgc3R5bGU9ImhlaWdodDowcHg7d2lkdGg6MHB4Ij48L2E+DQ0KPERJViBDTEFTUz0ic291cmNlIj48aT5PcmcuIFN5bnRoLjwvaT4gPGI+MjAxMTwvYj4sIDxpPjg4PC9pPiwgMzUzLTM2MzwvRElWPg0NCg0NDQo8ZGl2IGNsYXNzPSJzb3VyY2UiPkRPSTogMTAuMTUyMjcvb3Jnc3luLjA4OC4wMzUzPC9kaXY+PGRpdiBjbGFzcz0idGl0bGUiPjxTUEFOIENMQVNTPSJjaGVtbmFtZSI+VEFOREVNIE5VQ0xFT1BISUxJQzwvU1BBTj4gQURESVRJT04gLyBGUkFHTUVOVEFUSU9OIE9GIDxTUEFOIENMQVNTPSJjaGVtbmFtZSI+VklOWUxPR09VUyBBQ1lMIFRSSUZMQVRFUzogMi1NRVRIWUwtMi0oMS1PWE8tNS1IRVBUWU5ZTCktMSwzLURJVEhJQU5FPC9TUEFOPjwvRElWPg0NDQo8RElWIENMQVNTPSJkcmF3aW5nIj4NDQ0KPFRBQkxFIENMQVNTPSJwcmVwZHJhd2luZyI+DQ0NCjxUUj4NDQ0KPFREPjxJTUcgc3JjPSIvY29udGVudC9maWd1cmVzL3Y4OHAwMzUzLTEuZ2lmIiB3aWR0aD0iMzUzIiBoZWlnaHQ9IjE3OCI+PC9URD4NDQ0KPC9UUj4NDQ0KPC9UQUJMRT4NDQ0KPC9ESVY+DQ0NCjxESVYgQ0xBU1M9ImF1dGhvcnMiPg0NDQoJU3VibWl0dGVkIGJ5IE1hcmlsZGEgUC4gTGlzYm9hLCBUdW5nIFQuIEhvYW5nLCBhbmQgR3JlZ29yeSBCLiBEdWRsZXk8U1VQPjxTUEFOIENMQVNTPSJob3RzcG90IiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdyZWYxJykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij48QSB0YXJnZXQ9Il9zZWxmIiBocmVmPSJkZW1vLmFzcHg/cHJlcD12ODhwMDM1MyNyZWYxIj4xPC9BPjwvU1BBTj48L1NVUD4uPC9ESVY+DQ0NCjxESVYgQ0xBU1M9ImF1dGhvcnMiPg0NDQoJQ2hlY2tlZCBieSBKaW1taWUgV2VhdmVyIGFuZCBKb25hdGhhbiBFbGxtYW4uPC9ESVY+DQ0NCjxkaXYgY2xhc3M9J2F1dGhvcnMnPjwvZGl2PjxESVYgQ0xBU1M9InNlY3RoZWFkaW5nIj4xLiBQcm9jZWR1cmU8L0RJVj4NDQ0KPERJViBDTEFTUz0ic3RlcCI+DQ0NCjxESVYgQ0xBU1M9InN0ZXBwYXJhIj48Yj5DYXV0aW9uOjwvYj4gPGk+RXhlcmNpc2UgY2FyZSBpbiB0aGUgaGFuZGxpbmcgb2YgdHJpZmx1b3JvbWV0aGFuZXN1bGZvbmljIGFuaHlkcmlkZSAoY29ycm9zaXZlKSwgcHlyaWRpbmUgKGhhcm1mdWwgYnkgaW5oYWxhdGlvbiksIGFuZCBidXR5bGxpdGhpdW0gKGZsYW1tYWJsZSwgY29ycm9zaXZlKS48L2k+PC9ESVY+DQ0NCjwvRElWPg0NDQo8RElWIENMQVNTPSJzdGVwIj4NDQ0KPERJViBDTEFTUz0ic3RlcHBhcmEiPjxpPkEuPC9pPiA8U1BBTiBDTEFTUz0iY2hlbWljYWwiPjxTUEFOIENMQVNTPSJjaGVtbmFtZSI+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coanNMb2FkQ3BkKDE1ODczKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiIG9uY2xpY2s9ImpzU2hvd0NwZFRpcCgxNTg3Myk7Ij48aT4yLU1ldGh5bC0zLXRyaWZsdW9yb21ldGhhbnN1bGZvbnlsb3h5LWN5Y2xvaGV4LTItZW4tMS1vbmUuPC9pPjwvU1BBTj48L1NQQU4+PC9TUEFOPiA8aT5BbjwvaT4gb3Zlbi1kcmllZCAyLUwsIHRocmVlLW5lY2tlZCwgcm91bmQtYm90dG9tZWQgZmxhc2sgZXF1aXBwZWQgd2l0aCBhIDEgaW5jaCBvdmFsIG1hZ25ldGljIHN0aXIgYmFyLCBhIHJ1YmJlciBzZXB0dW0sIG5pdHJvZ2VuIGlubGV0IGFuZCB0aGVybW9tZXRlciBpcyBjaGFyZ2VkIHdpdGggMi1tZXRoeWwtMSwzLTxTUEFOIENMQVNTPSJjaGVtaWNhbCI+PFNQQU4gQ0xBU1M9ImNoZW1uYW1lIj48U1BBTiBDTEFTUz0iaG90c3BvdCIgb25tb3VzZW92ZXI9InRvb2x0aXAuc2hvdyhqc0xvYWRDcGQoMzUxOCkpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7IiBvbmNsaWNrPSJqc1Nob3dDcGRUaXAoMzUxOCk7Ij5jeWNsb2hleGFuZWRpb25lPC9TUEFOPjwvU1BBTj4gKDE1LjAgZywgMC4xMTUgbW9sLCAxLjAgZXF1aXYpPC9TUEFOPiA8U1BBTiBDTEFTUz0iaG90c3BvdCIgb25jbGljaz0iamF2YXNjcmlwdDpqc1Rvb2xUaXBHb3RvKCdub3RlMScpIiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdub3RlMScpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+KE5vdGUgMSk8L1NQQU4+LCA8U1BBTiBDTEFTUz0iY2hlbWljYWwiPjxTUEFOIENMQVNTPSJjaGVtbmFtZSI+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coanNMb2FkQ3BkKDI3MCkpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7IiBvbmNsaWNrPSJqc1Nob3dDcGRUaXAoMjcwKTsiPnB5cmlkaW5lPC9TUEFOPjwvU1BBTj4gKDE5LjAgbUwsIDAuMjMwIG1vbCwgMiBlcXVpdik8L1NQQU4+IDxTUEFOIENMQVNTPSJob3RzcG90IiBvbmNsaWNrPSJqYXZhc2NyaXB0OmpzVG9vbFRpcEdvdG8oJ25vdGUyJykiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ25vdGUyJykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij4oTm90ZSAyKTwvU1BBTj4gYW5kIG1ldGh5bGVuZSBjaGxvcmlkZSAoNzAwIG1MKSA8U1BBTiBDTEFTUz0iaG90c3BvdCIgb25jbGljaz0iamF2YXNjcmlwdDpqc1Rvb2xUaXBHb3RvKCdub3RlMycpIiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdub3RlMycpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+KE5vdGUgMyk8L1NQQU4+Lg0NDQoNDQ0KVGhlIHJlYWN0aW9uIG1peHR1cmUgaXMgbWFnbmV0aWNhbGx5IHN0aXJyZWQsIGNvb2xlZCBhdCAtNzggJiMxNzY7QyBmb3IgMjAgbWluIDxTUEFOIENMQVNTPSJob3RzcG90IiBvbmNsaWNrPSJqYXZhc2NyaXB0OmpzVG9vbFRpcEdvdG8oJ25vdGU0JykiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ25vdGU0JykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij4oTm90ZSA0KTwvU1BBTj4sIGFuZCA8U1BBTiBDTEFTUz0iY2hlbWljYWwiPjxTUEFOIENMQVNTPSJjaGVtbmFtZSI+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coanNMb2FkQ3BkKDY4MDUpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyIgb25jbGljaz0ianNTaG93Q3BkVGlwKDY4MDUpOyI+dHJpZmx1b3JvbWV0aGFuZXN1bGZvbmljIGFuaHlkcmlkZTwvU1BBTj48L1NQQU4+ICgyMy41IG1MLCAwLjEzOCBtb2wsIDEuMiBlcXVpdik8L1NQQU4+IDxTUEFOIENMQVNTPSJob3RzcG90IiBvbmNsaWNrPSJqYXZhc2NyaXB0OmpzVG9vbFRpcEdvdG8oJ25vdGUxJykiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ25vdGUxJykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij4oTm90ZSAxKTwvU1BBTj4gaXMgYWRkZWQgZHJvcHdpc2UgdmlhIHN5cmluZ2Ugb3ZlciAxMCBtaW4gKE5vdGVzIDxTUEFOIENMQVNTPSJob3RzcG90IiBvbmNsaWNrPSJqYXZhc2NyaXB0OmpzVG9vbFRpcEdvdG8oJ25vdGU1JykiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ25vdGU1JykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij41PC9TUEFOPiBhbmQgPFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9uY2xpY2s9ImphdmFzY3JpcHQ6anNUb29sVGlwR290bygnbm90ZTYnKSIgb25tb3VzZW92ZXI9InRvb2x0aXAuc2hvdyhnZXRJdGVtVGV4dCgnbm90ZTYnKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiPjY8L1NQQU4+KS4NDQ0KDQ0NClRoZSBsaWdodCB5ZWxsb3cgcmVhY3Rpb24gbWl4dHVyZSBpcyBzdGlycmVkIGF0IC03OCAmIzE3NjtDIGZvciAyMCBtaW4sIGF0IDAgJiMxNzY7QyBmb3IgMjAgbWluLCBhbmQgYXQgcm9vbSB0ZW1wZXJhdHVyZSBmb3IgMzAgbWluIDxTUEFOIENMQVNTPSJob3RzcG90IiBvbmNsaWNrPSJqYXZhc2NyaXB0OmpzVG9vbFRpcEdvdG8oJ25vdGU0JykiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ25vdGU0JykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij4oTm90ZSA0KTwvU1BBTj4sIGF0IHdoaWNoIHRpbWUgdGhlIHJlYWN0aW9uIG1peHR1cmUgaXMgYSBob21vZ2VuZW91cyByZWQgc29sdXRpb24uDQ0NCg0NDQpUaGUgcmVhY3Rpb24gbWl4dHVyZSBpcyBhY2lkaWZpZWQgdXNpbmcgMjAwIG1MIG9mIGEgMU0gYXF1ZW91cyBzb2x1dGlvbiBvZiBoeWRyb2NobG9yaWMgYWNpZCA8U1BBTiBDTEFTUz0iaG90c3BvdCIgb25jbGljaz0iamF2YXNjcmlwdDpqc1Rvb2xUaXBHb3RvKCdub3RlNycpIiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdub3RlNycpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+KE5vdGUgNyk8L1NQQU4+LCBhbmQgdGhlIHJlc3VsdGluZyBiaXBoYXNpYyBzb2x1dGlvbiBpcyB0cmFuc2ZlcnJlZCB0byBhIDItTCBzZXBhcmF0b3J5IGZ1bm5lbC4NDQ0KDQ0NClRoZSBvcmdhbmljIHBoYXNlIGlzIHJlbW92ZWQsIGFuZCB0aGUgYXF1ZW91cyBsYXllciBpcyBleHRyYWN0ZWQgd2l0aCA8U1BBTiBDTEFTUz0iY2hlbWljYWwiPjxTUEFOIENMQVNTPSJjaGVtbmFtZSI+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coanNMb2FkQ3BkKDE3KSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiIG9uY2xpY2s9ImpzU2hvd0NwZFRpcCgxNyk7Ij5kaWV0aHlsIGV0aGVyPC9TUEFOPjwvU1BBTj4gKDMgeCAyMDAgbUwpPC9TUEFOPiA8U1BBTiBDTEFTUz0iaG90c3BvdCIgb25jbGljaz0iamF2YXNjcmlwdDpqc1Rvb2xUaXBHb3RvKCdub3RlOCcpIiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdub3RlOCcpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+KE5vdGUgOCk8L1NQQU4+Lg0NDQoNDQ0KVGhlIG9yZ2FuaWMgcGhhc2VzIGFyZSBjb21iaW5lZCBhbmQgZHJpZWQgb3ZlciAxMDAgZyBvZiBOYTxzdWI+Mjwvc3ViPlNPPHN1Yj40PC9zdWI+IGFuZCBmaWx0ZXJlZCBieSB2YWN1dW0gc3VjdGlvbiB0aHJvdWdoIGEgbWVkaXVtIHBvcm9zaXR5IGZyaXR0ZWQgZ2xhc3MgZnVubmVsLCBhbmQgdGhlIHNvbHZlbnQgaXMgcmVtb3ZlZCB1bmRlciByZWR1Y2VkIHByZXNzdXJlIGJ5IHJvdGFyeSBldmFwb3JhdGlvbiAoMjUtNDUgbW1IZywgcm9vbSB0ZW1wZXJhdHVyZSB3YXRlciBiYXRoKSBwcm92aWRpbmcgdGhlIGNydWRlIHByb2R1Y3QgYXMgYSByZWQgb2lsIDxTUEFOIENMQVNTPSJob3RzcG90IiBvbmNsaWNrPSJqYXZhc2NyaXB0OmpzVG9vbFRpcEdvdG8oJ25vdGU5JykiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ25vdGU5JykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij4oTm90ZSA5KTwvU1BBTj4uDQ0NCg0NDQpUaGUgY3J1ZGUgcHJvZHVjdCBpcyBwdXJpZmllZCBieSBjaHJvbWF0b2dyYXBoeSBvbiBzaWxpY2EgZ2VsIDxTUEFOIENMQVNTPSJob3RzcG90IiBvbmNsaWNrPSJqYXZhc2NyaXB0OmpzVG9vbFRpcEdvdG8oJ25vdGUxMCcpIiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdub3RlMTAnKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiPihOb3RlIDEwKTwvU1BBTj4gdG8gYWZmb3JkIDMwLjAgZyAoOTglKSBvZiB0aGUgcHJvZHVjdCBhcyBhIGNvbG9ybGVzcyBvaWwgPFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9uY2xpY2s9ImphdmFzY3JpcHQ6anNUb29sVGlwR290bygnbm90ZTExJykiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ25vdGUxMScpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+KE5vdGUgMTEpPC9TUEFOPi4NDQ0KDQ0NCjItTWV0aHlsLTMtdHJpZmx1b3JvbWV0aGFuc3VsZm9ueWxveHktY3ljbG9oZXgtMi1lbi0xLW9uZSBpcyBpbmRlZmluaXRlbHkgc3RhYmxlIHRvIHN0b3JhZ2UgdW5kZXIgbml0cm9nZW4gYXQgLTEzICYjMTc2O0MuPC9ESVY+DQ0NCjwvRElWPg0NDQo8RElWIENMQVNTPSJzdGVwIj4NDQ0KPERJViBDTEFTUz0ic3RlcHBhcmEiPjxpPkIuPC9pPiA8U1BBTiBDTEFTUz0iY2hlbWljYWwiPjxTUEFOIENMQVNTPSJjaGVtbmFtZSI+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coanNMb2FkQ3BkKDE1ODc0KSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiIG9uY2xpY2s9ImpzU2hvd0NwZFRpcCgxNTg3NCk7Ij48aT4yLU1ldGh5bC0yLSgxLW94by01LWhlcHR5bnlsKS0xLDMtZGl0aGlhbmUuPC9pPjwvU1BBTj48L1NQQU4+PC9TUEFOPiBBbiBvdmVuLWRyaWVkIHR3by1uZWNrZWQsIDUwMC1tTCwgcm91bmQtYm90dG9tZWQgZmxhc2sgZXF1aXBwZWQgd2l0aCAwLjUgaW5jaCBvdmFsIG1hZ25ldGljIHN0aXIgYmFyLCBydWJiZXIgc2VwdHVtLCBhbmQgYSBuaXRyb2dlbiBpbmxldCBhZGFwdGVyIGlzIGNoYXJnZWQgd2l0aCAyLW1ldGh5bC0xLDMtZGl0aGlhbmUgPFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9uY2xpY2s9ImphdmFzY3JpcHQ6anNUb29sVGlwR290bygnbm90ZTEyJykiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ25vdGUxMicpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+KE5vdGUgMTIpPC9TUEFOPiAoNC42NCBtTCwgMzguNyBtbW9sLCAxLjEgZXF1aXYpIGFuZCB0ZXRyYWh5ZHJvZnVyYW4gKDE1MCBtTCkgPFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9uY2xpY2s9ImphdmFzY3JpcHQ6anNUb29sVGlwR290bygnbm90ZTEzJykiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ25vdGUxMycpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+KE5vdGUgMTMpPC9TUEFOPi4NDQ0KDQ0NClRoZSByZXN1bHRpbmcgc29sdXRpb24gaXMgY29vbGVkIGF0IC03OCAmIzE3NjtDIDxTUEFOIENMQVNTPSJob3RzcG90IiBvbmNsaWNrPSJqYXZhc2NyaXB0OmpzVG9vbFRpcEdvdG8oJ25vdGU0JykiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ25vdGU0JykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij4oTm90ZSA0KTwvU1BBTj4uDQ0NCg0NDQpBIHNvbHV0aW9uIG9mIDxpPm48L2k+LWJ1dHlsbGl0aGl1bSA8U1BBTiBDTEFTUz0iaG90c3BvdCIgb25jbGljaz0iamF2YXNjcmlwdDpqc1Rvb2xUaXBHb3RvKCdub3RlMTQnKSIgb25tb3VzZW92ZXI9InRvb2x0aXAuc2hvdyhnZXRJdGVtVGV4dCgnbm90ZTE0JykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij4oTm90ZSAxNCk8L1NQQU4+ICgxNC41IG1MLCAzNS4yIG1tb2wsIDEuMCBlcXVpdikgaXMgYWRkZWQgZHJvcHdpc2UgdmlhIHN5cmluZ2Ugb3ZlciAxMCBtaW4gPFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9uY2xpY2s9ImphdmFzY3JpcHQ6anNUb29sVGlwR290bygnbm90ZTE1JykiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ25vdGUxNScpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+KE5vdGUgMTUpPC9TUEFOPi4NDQ0KDQ0NClRoZSBsaWdodCB5ZWxsb3cgcmVhY3Rpb24gbWl4dHVyZSBpcyBzdGlycmVkIGF0IC03OCAmIzE3NjtDIGZvciAyMCBtaW4sIGF0IDAgJiMxNzY7QyBmb3IgMTAgbWluLCBhbmQgYXQgLTMwICYjMTc2O0MgZm9yIDE1IG1pbiA8U1BBTiBDTEFTUz0iaG90c3BvdCIgb25jbGljaz0iamF2YXNjcmlwdDpqc1Rvb2xUaXBHb3RvKCdub3RlNCcpIiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdub3RlNCcpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+KE5vdGUgNCk8L1NQQU4+LCBhbmQgdGhlbiA8U1BBTiBDTEFTUz0iY2hlbWljYWwiPjxTUEFOIENMQVNTPSJjaGVtbmFtZSI+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coanNMb2FkQ3BkKDE1ODczKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiIG9uY2xpY2s9ImpzU2hvd0NwZFRpcCgxNTg3Myk7Ij4yLW1ldGh5bC0zLXRyaWZsdW9yb21ldGhhbmVzdWxmb255bG94eS1jeWNsb2hleC0yLWVuLTEtb25lPC9TUEFOPjwvU1BBTj4gKDEwLjAgZywgMzguNyBtbW9sLCAxLjEgZXF1aXYpPC9TUEFOPiBpcyBhZGRlZCBkcm9wd2lzZSBieSBzeXJpbmdlIG92ZXIgMTAgbWluLg0NDQoNDQ0KVGhlIGxpZ2h0IHllbGxvdyByZWFjdGlvbiBtaXh0dXJlIGlzIHN0aXJyZWQgYXQgLTMwICYjMTc2O0MgZm9yIDE1IG1pbiwgYXQgMCAmIzE3NjtDIGZvciAxNSBtaW4sIGFuZCBhdCByb29tIHRlbXBlcmF0dXJlIGZvciAzMCBtaW4gPFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9uY2xpY2s9ImphdmFzY3JpcHQ6anNUb29sVGlwR290bygnbm90ZTQnKSIgb25tb3VzZW92ZXI9InRvb2x0aXAuc2hvdyhnZXRJdGVtVGV4dCgnbm90ZTQnKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiPihOb3RlIDQpPC9TUEFOPiwgYXQgd2hpY2ggdGltZSB0aGUgcmVhY3Rpb24gbWl4dHVyZSBpcyBhIGhvbW9nZW5lb3VzIHJlZCBzb2x1dGlvbiA8U1BBTiBDTEFTUz0iaG90c3BvdCIgb25jbGljaz0iamF2YXNjcmlwdDpqc1Rvb2xUaXBHb3RvKCdub3RlMTYnKSIgb25tb3VzZW92ZXI9InRvb2x0aXAuc2hvdyhnZXRJdGVtVGV4dCgnbm90ZTE2JykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij4oTm90ZSAxNik8L1NQQU4+Lg0NDQoNDQ0KQSBoYWxmLXNhdHVyYXRlZCBzb2x1dGlvbiBvZiA8U1BBTiBDTEFTUz0iY2hlbWljYWwiPjxTUEFOIENMQVNTPSJjaGVtbmFtZSI+YXF1ZW91cyBhbW1vbml1bSBjaGxvcmlkZTwvU1BBTj4gKDEwMCBtTCk8L1NQQU4+IDxTUEFOIENMQVNTPSJob3RzcG90IiBvbmNsaWNrPSJqYXZhc2NyaXB0OmpzVG9vbFRpcEdvdG8oJ25vdGUxNycpIiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdub3RlMTcnKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiPihOb3RlIDE3KTwvU1BBTj4gaXMgdGhlbiBhZGRlZCBhbmQgdGhlIGJpcGhhc2ljIHNvbHV0aW9uIGlzIHRyYW5zZmVycmVkIHRvIGEgNTAwLW1MIHNlcGFyYXRvcnkgZnVubmVsIGFuZCBleHRyYWN0ZWQgd2l0aCA8U1BBTiBDTEFTUz0iY2hlbWljYWwiPjxTUEFOIENMQVNTPSJjaGVtbmFtZSI+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coanNMb2FkQ3BkKDE3KSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiIG9uY2xpY2s9ImpzU2hvd0NwZFRpcCgxNyk7Ij5kaWV0aHlsIGV0aGVyPC9TUEFOPjwvU1BBTj4gKDMgeCA1MCBtTCk8L1NQQU4+IDxTUEFOIENMQVNTPSJob3RzcG90IiBvbmNsaWNrPSJqYXZhc2NyaXB0OmpzVG9vbFRpcEdvdG8oJ25vdGU4JykiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ25vdGU4JykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij4oTm90ZSA4KTwvU1BBTj4uDQ0NCg0NDQpUaGUgb3JnYW5pYyBwaGFzZXMgYXJlIGNvbWJpbmVkIGFuZCBkcmllZCBvdmVyIDcwIGcgb2YgTmE8c3ViPjI8L3N1Yj5TTzxzdWI+NDwvc3ViPiwgZmlsdGVyZWQgYnkgdmFjdXVtIHN1Y3Rpb24gdGhyb3VnaCBhIG1lZGl1bSBwb3Jvc2l0eSBmcml0dGVkIGdsYXNzIGZ1bm5lbCwgYW5kIHRoZSBzb2x2ZW50IGlzIHJlbW92ZWQgdW5kZXIgcmVkdWNlZCBwcmVzc3VyZSBieSByb3RhcnkgZXZhcG9yYXRpb24gKDI1LTQ1IG1tSGcsIHJvb20gdGVtcGVyYXR1cmUgd2F0ZXIgYmF0aCkgcHJvdmlkaW5nIHRoZSBjcnVkZSBwcm9kdWN0IGFzIGEgeWVsbG93IG9pbC4NDQ0KDQ0NClRoZSBjcnVkZSBwcm9kdWN0IGlzIHB1cmlmaWVkIGJ5IGNocm9tYXRvZ3JhcGh5IG9uIHNpbGljYSBnZWwgPFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9uY2xpY2s9ImphdmFzY3JpcHQ6anNUb29sVGlwR290bygnbm90ZTE4JykiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ25vdGUxOCcpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+KE5vdGUgMTgpPC9TUEFOPiB0byBhZmZvcmQgNi42NCBnICg3MSUpIDxTUEFOIENMQVNTPSJob3RzcG90IiBvbmNsaWNrPSJqYXZhc2NyaXB0OmpzVG9vbFRpcEdvdG8oJ25vdGUxOScpIiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdub3RlMTknKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiPihOb3RlIDE5KTwvU1BBTj4gb2YgdGhlIHByb2R1Y3QgYXMgYSBjb2xvcmxlc3Mgb2lsIDxTUEFOIENMQVNTPSJob3RzcG90IiBvbmNsaWNrPSJqYXZhc2NyaXB0OmpzVG9vbFRpcEdvdG8oJ25vdGUyMCcpIiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdub3RlMjAnKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiPihOb3RlIDIwKTwvU1BBTj4uPC9ESVY+DQ0NCjwvRElWPg0NDQo8RElWIENMQVNTPSJzZWN0aGVhZGluZyI+Mi4gTm90ZXM8L0RJVj4NDQ0KPERJViBDTEFTUz0ibm90ZXNib2RpZXMiPg0NDQo8RElWIGNsYXNzPSJub3RlcGFyYSI+PEEgbmFtZT0ibm90ZTEiIGlkPSJub3RlMSI+PC9BPjEuDQ0NCgk8U1BBTiBDTEFTUz0iY2hlbWljYWwiPjxTUEFOIENMQVNTPSJjaGVtbmFtZSI+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coanNMb2FkQ3BkKDU0NDUpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyIgb25jbGljaz0ianNTaG93Q3BkVGlwKDU0NDUpOyI+Mi1NZXRoeWwtMSwzLWN5Y2xvaGV4YW5lZGlvbmU8L1NQQU4+PC9TUEFOPiAoOTclKTwvU1BBTj4gYW5kIDxTUEFOIENMQVNTPSJjaGVtaWNhbCI+PFNQQU4gQ0xBU1M9ImNoZW1uYW1lIj48U1BBTiBDTEFTUz0iaG90c3BvdCIgb25tb3VzZW92ZXI9InRvb2x0aXAuc2hvdyhqc0xvYWRDcGQoNjgwNSkpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7IiBvbmNsaWNrPSJqc1Nob3dDcGRUaXAoNjgwNSk7Ij50cmlmbHVvcm9tZXRoYW5lLXN1bGZvbmljIGFuaHlkcmlkZTwvU1BBTj48L1NQQU4+ICg5OSUpPC9TUEFOPiB3ZXJlIHB1cmNoYXNlZCBmcm9tIFNpZ21hLUFsZHJpY2ggYW5kIHVzZWQgd2l0aG91dCBmdXJ0aGVyIHB1cmlmaWNhdGlvbi48L0RJVj4NDQ0KDQ0NCjxESVYgY2xhc3M9Im5vdGVwYXJhIj48QSBuYW1lPSJub3RlMiIgaWQ9Im5vdGUyIj48L0E+Mi4NDQ0KCTxTUEFOIENMQVNTPSJjaGVtaWNhbCI+PFNQQU4gQ0xBU1M9ImNoZW1uYW1lIj48U1BBTiBDTEFTUz0iaG90c3BvdCIgb25tb3VzZW92ZXI9InRvb2x0aXAuc2hvdyhqc0xvYWRDcGQoMjcwKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiIG9uY2xpY2s9ImpzU2hvd0NwZFRpcCgyNzApOyI+UHlyaWRpbmU8L1NQQU4+PC9TUEFOPiAoOTklKTwvU1BBTj4gd2FzIHB1cmNoYXNlZCBmcm9tIFNpZ21hLUFsZHJpY2ggYW5kIHN0b3JlZCBvdmVyIEtPSCBwZWxsZXRzLjwvRElWPg0NDQoNDQ0KPERJViBjbGFzcz0ibm90ZXBhcmEiPjxBIG5hbWU9Im5vdGUzIiBpZD0ibm90ZTMiPjwvQT4zLg0NDQoJTWV0aHlsZW5lIGNobG9yaWRlIChIUExDIEdyYWRlKSB3YXMgcHVyY2hhc2VkIGZyb20gRmlzY2hlciBTY2llbnRpZmljIGFuZCBwdXJpZmllZCB1c2luZyBhbiBJbm5vdmF0aXZlIFRlY2hub2xvZ3kgc29sdmVudCBwdXJpZmljYXRpb24gc3lzdGVtLjwvRElWPg0NDQoNDQ0KPERJViBjbGFzcz0ibm90ZXBhcmEiPjxBIG5hbWU9Im5vdGU0IiBpZD0ibm90ZTQiPjwvQT40Lg0NDQoJVGhlIGluZGljYXRlZCB0ZW1wZXJhdHVyZXMgYXQgd2hpY2ggcmVhY3Rpb24gbWl4dHVyZXMgYXJlIGtlcHQgcmVmZXIgdG8gdGhlIHRlbXBlcmF0dXJlIG9mIGV4dGVybmFsIGNvb2xpbmcgYmF0aHMgYXMgZm9sbG93czogKGEpIC03OCAmIzE3NjtDIGNvb2xpbmcgYmF0aCBwcmVwYXJlZCB3aXRoIGRyeSBpY2UgYW5kIGFjZXRvbmUsIChiKSAwICYjMTc2O0MgY29vbGluZyBiYXRoIHByZXBhcmVkIHdpdGggaWNlIGFuZCB3YXRlciwgYW5kIChjKSAtMzAgJiMxNzY7QyBjb29saW5nIGJhdGggcHJlcGFyZWQgYnkgYWRkaW5nIGRyeSBpY2UgdG8gYWNldG9uZSBhbmQgY2FyZWZ1bGx5IG1vbml0b3JpbmcgdGhlIGJhdGggdGVtcGVyYXR1cmUuDQ0NCg0NDQpObyBleHRlcm5hbCBiYXRoIHdhcyBlbXBsb3llZCBmb3IgcmVhY3Rpb25zIGNvbmR1Y3RlZCBhdCByb29tIHRlbXBlcmF0dXJlLjwvRElWPg0NDQoNDQ0KPERJViBjbGFzcz0ibm90ZXBhcmEiPjxBIG5hbWU9Im5vdGU1IiBpZD0ibm90ZTUiPjwvQT41Lg0NDQoJVGhlIGhpZ2hlc3QgaW50ZXJuYWwgdGVtcGVyYXR1cmUgb2JzZXJ2ZWQgYnkgdGhlIGNoZWNrZXJzIHdhcyANDQ0KDQ0NCi02MSAmIzE3NjtDLjwvRElWPg0NDQoNDQ0KPERJViBjbGFzcz0ibm90ZXBhcmEiPjxBIG5hbWU9Im5vdGU2IiBpZD0ibm90ZTYiPjwvQT42Lg0NDQoJVGhlIHN1Ym1pdHRlcnMgb2JzZXJ2ZWQgdGhhdCBhIHNtYWxsIGFtb3VudCBvZiB3aGl0ZSBwcmVjaXBpdGF0ZSBmb3JtcyBkdXJpbmcgdGhlIGFkZGl0aW9uIG9mIHRyaWZsdW9yb21ldGhhbmVzdWxmb25pYyBhbmh5ZHJpZGUuPC9ESVY+DQ0NCg0NDQo8RElWIGNsYXNzPSJub3RlcGFyYSI+PEEgbmFtZT0ibm90ZTciIGlkPSJub3RlNyI+PC9BPjcuDQ0NCglIeWRyb2NobG9yaWMgYWNpZCAoMSBNKSB3YXMgcHJlcGFyZWQgYnkgZGlsdXRpb24gb2YgaHlkcm9jaGxvcmljIGFjaWQgKDEyLjEgTSwgQUNTIGdyYWRlKSBwdXJjaGFzZWQgZnJvbSBFTUQgQ2hlbWljYWxzLjwvRElWPg0NDQoNDQ0KPERJViBjbGFzcz0ibm90ZXBhcmEiPjxBIG5hbWU9Im5vdGU4IiBpZD0ibm90ZTgiPjwvQT44Lg0NDQoJRXRoeWwgZXRoZXIgKGFuaHlkcm91cywgQUNTIGdyYWRlKSB3YXMgcHVyY2hhc2VkIGZyb20gRU1EIENoZW1pY2FscyBhbmQgdXNlZCB3aXRob3V0IGZ1cnRoZXIgcHVyaWZpY2F0aW9uLjwvRElWPg0NDQoNDQ0KPERJViBjbGFzcz0ibm90ZXBhcmEiPjxBIG5hbWU9Im5vdGU5IiBpZD0ibm90ZTkiPjwvQT45Lg0NDQoJVGhlIHN1Ym1pdHRlcnMgb2J0YWluZWQgYSB5ZWxsb3cgb2lsLjwvRElWPg0NDQoNDQ0KPERJViBjbGFzcz0ibm90ZXBhcmEiPjxBIG5hbWU9Im5vdGUxMCIgaWQ9Im5vdGUxMCI+PC9BPjEwLg0NDQoJVGhlIGNydWRlIHByb2R1Y3Qgd2FzIHB1cmlmaWVkIHVzaW5nIDMwMCBnIG9mIFNpbGljYSBHZWwgNjAgKEdlZHVyYW4ocikgNDAtNjMgJiMxODE7TSkgd2V0LWxvYWRlZCBhcyBhIHNsdXJyeS4NDQ0KDQ0NClRoZSBzYW1wbGUgd2FzIGxvYWRlZCBpbiBhIG1pbmltdW0gdm9sdW1lIG9mIGVsdWVudCwgcGFzc2VkIHRocm91Z2ggdGhlIGNvbHVtbiB1c2luZyBncmFkaWVudCA8U1BBTiBDTEFTUz0iY2hlbWljYWwiPjxTUEFOIENMQVNTPSJjaGVtbmFtZSI+ZWx1dGlvbjwvU1BBTj4gKDUwMCBtTCBvZiA5OjEgaGV4YW5lczpFdE9BYywgNTAwIG1MIG9mIDg6MiBoZXhhbmVzOkV0T0FjLCBhbmQgMTAwMCBtTCBvZiA3OjMgaGV4YW5lczpFdE9BYyk8L1NQQU4+LCBhbmQgY29sbGVjdGVkIGluIDIwLW1MIGZyYWN0aW9ucy4NDQ0KDQ0NCkZyYWN0aW9ucyA1OC05OSB3ZXJlIGNvbGxlY3RlZCwgY29tYmluZWQsIGFuZCBjb25jZW50cmF0ZWQgdW5kZXIgcmVkdWNlZCBwcmVzc3VyZSB0byBvYnRhaW4gdGhlIGZpbmFsIHByb2R1Y3QuDQ0NCg0NDQpUaGUgUjxzdWI+Zjwvc3ViPiBvZiAyLW1ldGh5bC0zLXRyaWZsdW9yb21ldGhhbnN1bGZvbnlsb3h5LWN5Y2xvaGV4LTItZW4tMS1vbmUgPSAwLjYyIGFuZCAyLW1ldGh5bC0xLDMtY3ljbG9oZXhhbmVkaW9uZSA9IDAuMjIgaW4gODoyIGhleGFuZXM6ZXRoeWwgYWNldGF0ZS48L0RJVj4NDQ0KDQ0NCjxESVYgY2xhc3M9Im5vdGVwYXJhIj48QSBuYW1lPSJub3RlMTEiIGlkPSJub3RlMTEiPjwvQT4xMS4NDQ0KCVRoZSBjb21wb3VuZCBleGhpYml0ZWQgdGhlIGZvbGxvd2luZyBwaHlzaWNhbCBhbmQgc3BlY3Ryb3Njb3BpYyBkYXRhOiBJUiAobmVhdCk6IDI5NjQsIDE2ODgsIDE0MTYsIDEzNDQsIDEyMTAsIDExMzUsIDEwMjQsIDkxMiwgODkxLCA3OTMsIDc1OSBjbTxzdXA+LTE8L3N1cD4uDQ0NCg0NDQo8c3VwPjE8L3N1cD5IIE5NUiA8QSBDTEFTUz0icGRmbGluayIgdGFyZ2V0PSJfYmxhbmsiIGhyZWY9Ii9jb250ZW50L3BkZnMvU3BlY3RydW0vdjg4cDAzNTNfSF9ub3RlMTEucGRmIj5wZGY8L0E+KDUwMCBNSHosIENEQ2w8c3ViPjM8L3N1Yj4pICYjOTQ4OzogMS43NyAoZCwgPGk+SjwvaT4gPSAxLjkgSHosIDMgSCksIDIuMDUgLSAxLjk3IChhcHBhcmVudCBwZW50ZXQsIDIgSCksIDIuNDAgKHQsIDxpPko8L2k+ID0gNy45IEh6LCAyIEgpLCAyLjY2IChkdGQsIDxpPko8L2k+ID0gNi4xLCA0LjAsIDEuOSBIeiwgMiBIKTsgPHN1cD4xMzwvc3VwPkMgTk1SIDxBIENMQVNTPSJwZGZsaW5rIiB0YXJnZXQ9Il9ibGFuayIgaHJlZj0iL2NvbnRlbnQvcGRmcy9TcGVjdHJ1bS92ODhwMDM1M19DX25vdGUxMS5wZGYiPnBkZjwvQT4oMTI2IE1IeiwgQ0RDbDxzdWI+Mzwvc3ViPikgJiM5NDg7OiA5LjAsIDIwLjUsIDI4LjYsIDM2LjUsIDExOC4yIChxLCA8aT5KPC9pPjxzdWI+Q0Y8L3N1Yj4gPSAzMTkuOCBIeiksIDEyNy45LCAxNjIuMCwgMTk3LjU7IEhSTVMgKEVTSSkgY2FsY2QuDQ0NCg0NDQpmb3IgQzxzdWI+ODwvc3ViPkg8c3ViPjk8L3N1Yj5IRjxzdWI+Mzwvc3ViPk88c3ViPjQ8L3N1Yj5TW00rSF06IDI1OS4wMjQ2Lg0NDQoNDQ0KRm91bmQ6IDI1OS4wMjQ2Lg0NDQoNDQ0KQW5hbC4NDQ0KDQ0NCmNhbGNkLg0NDQoNDQ0KZm9yIEM8c3ViPjg8L3N1Yj5IPHN1Yj45PC9zdWI+RjxzdWI+Mzwvc3ViPk88c3ViPjQ8L3N1Yj5TOiBDLCAzNy4yMTsgSCwgMy41MTsgRiwgMjIuMDc7IFMsIDEyLjQyLg0NDQoNDQ0KRm91bmQ6IEMsIDM3LjMyOyBILCAzLjQ1OyBGLCAyMS44NDsgUywgMTIuNDEuPC9ESVY+DQ0NCg0NDQo8RElWIGNsYXNzPSJub3RlcGFyYSI+PEEgbmFtZT0ibm90ZTEyIiBpZD0ibm90ZTEyIj48L0E+MTIuDQ0NCgk8U1BBTiBDTEFTUz0iY2hlbWljYWwiPjxTUEFOIENMQVNTPSJjaGVtbmFtZSI+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coanNMb2FkQ3BkKDE1ODc1KSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiIG9uY2xpY2s9ImpzU2hvd0NwZFRpcCgxNTg3NSk7Ij4yLU1ldGh5bC0xLDMtZGl0aGlhbmU8L1NQQU4+PC9TUEFOPiAoPTk4JSk8L1NQQU4+IHdhcyBwdXJjaGFzZWQgZnJvbSBGbHVrYSBhbmQgdXNlZCB3aXRob3V0IGZ1cnRoZXIgcHVyaWZpY2F0aW9uLjwvRElWPg0NDQoNDQ0KPERJViBjbGFzcz0ibm90ZXBhcmEiPjxBIG5hbWU9Im5vdGUxMyIgaWQ9Im5vdGUxMyI+PC9BPjEzLg0NDQoJVGV0cmFoeWRyb2Z1cmFuIChIUExDIEdyYWRlKSB3YXMgcHVyY2hhc2VkIGZyb20gRU1EIENoZW1pY2FscyBhbmQgcHVyaWZpZWQgdXNpbmcgYW4gSW5ub3ZhdGl2ZSBUZWNobm9sb2d5IHNvbHZlbnQgcHVyaWZpY2F0aW9uIHN5c3RlbS48L0RJVj4NDQ0KDQ0NCjxESVYgY2xhc3M9Im5vdGVwYXJhIj48QSBuYW1lPSJub3RlMTQiIGlkPSJub3RlMTQiPjwvQT4xNC4NDQ0KCTxpPm48L2k+LUJ1dHlsbGl0aGl1bSAoMi41IE0gc29sdXRpb24gaW4gaGV4YW5lcykgd2FzIHB1cmNoYXNlZCBmcm9tIFNpZ21hLUFsZHJpY2ggYW5kIHRpdHJhdGVkIHVzaW5nICgtKS1tZW50aG9sIGFuZCAxLDEwLXBoZW5hbnRocm9saW5lICg9IDk5JSkuPC9ESVY+DQ0NCg0NDQo8RElWIGNsYXNzPSJub3RlcGFyYSI+PEEgbmFtZT0ibm90ZTE1IiBpZD0ibm90ZTE1Ij48L0E+MTUuDQ0NCglUaGUgaW50ZXJuYWwgdGVtcGVyYXR1cmUgcmVhY2hlZCAtNTcgJiMxNzY7QyBkdXJpbmcgYWRkaXRpb24uPC9ESVY+DQ0NCg0NDQo8RElWIGNsYXNzPSJub3RlcGFyYSI+PEEgbmFtZT0ibm90ZTE2IiBpZD0ibm90ZTE2Ij48L0E+MTYuDQ0NCglUTEMgYW5hbHlzaXMgc2hvd2VkIGZvcm1hdGlvbiBvZiBwcm9kdWN0IGJ5IFRMQyAoUjxpPjxzdWI+Zjwvc3ViPjwvaT4gKHJlYWN0aW9uIHByb2R1Y3QpID0gMC4zOyBSPGk+PHN1Yj5mPC9zdWI+PC9pPiAoMi1tZXRoeWwtMSwzLWRpdGhpYW5lKSA9IDAuNDAsIFI8aT48c3ViPmY8L3N1Yj48L2k+ICgyLW1ldGh5bC0zLXRyaWZsdW9yb21ldGhhbnN1bGZvbnlsb3h5LWN5Y2xvaGV4LTItZW4tMS1vbmUpID0gMC4yOyBlbHV0aW9uIHdpdGggOToxIGhleGFuZXM6RXRPQWM7IFVWIGFuZCBLTW5PPHN1Yj40PC9zdWI+L2hlYXRpbmcgdmlzdWFsaXphdGlvbikuDQ0NCg0NDQpDb21wbGV0aW9uIG9mIHRoZSByZWFjdGlvbiBpcyBkaWZmaWN1bHQgdG8gZGlzY2VybiBiZWNhdXNlIDxpPm48L2k+LWJ1dHlsbGl0aGl1bSBpcyB0aGUgbGltaXRpbmcgcmVhZ2VudCwgYW5kIHRoZXJlZm9yZSBib3RoIHRoZSBkaXRoaWFuZSBhbmQgdHJpZmxhdGUgcmVtYWluIGV2ZW4gYWZ0ZXIgYWxsIG9mIHRoZSBidXR5bGxpdGhpdW0gaGFzIGJlZW4gY29uc3VtZWQuPC9ESVY+DQ0NCg0NDQo8RElWIGNsYXNzPSJub3RlcGFyYSI+PEEgbmFtZT0ibm90ZTE3IiBpZD0ibm90ZTE3Ij48L0E+MTcuDQ0NCglIYWxmLXNhdHVyYXRlZCBhcXVlb3VzIGFtbW9uaXVtIGNobG9yaWRlIHNvbHV0aW9uIHdhcyBwcmVwYXJlZCBieSBkaWx1dGlvbiBvZiBhIHNhdHVyYXRlZCBhcXVlb3VzIGFtbW9uaXVtIGNobG9yaWRlIHNvbHV0aW9uOyA8U1BBTiBDTEFTUz0iY2hlbWljYWwiPjxTUEFOIENMQVNTPSJjaGVtbmFtZSI+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coanNMb2FkQ3BkKDIwKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiIG9uY2xpY2s9ImpzU2hvd0NwZFRpcCgyMCk7Ij5hbW1vbml1bSBjaGxvcmlkZTwvU1BBTj48L1NQQU4+ICg5OS41JSBBQ1MpPC9TUEFOPiByZWFnZW50IHB1cmNoYXNlZCBmcm9tIFNpZ21hLUFsZHJpY2guPC9ESVY+DQ0NCg0NDQo8RElWIGNsYXNzPSJub3RlcGFyYSI+PEEgbmFtZT0ibm90ZTE4IiBpZD0ibm90ZTE4Ij48L0E+MTguDQ0NCglUaGUgY3J1ZGUgcHJvZHVjdCB3YXMgcHVyaWZpZWQgdXNpbmcgMzAwIGcgb2YgU2lsaWNhIEdlbCA2MCAoR2VkdXJhbihyKSA0MC02MyAmIzE4MTtNKSB3ZXQtbG9hZGVkIGFzIGEgc2x1cnJ5Lg0NDQoNDQ0KVGhlIHNhbXBsZSB3YXMgbG9hZGVkIGluIGEgbWluaW11bSB2b2x1bWUgb2YgZWx1ZW50LCBwYXNzZWQgdGhyb3VnaCB0aGUgY29sdW1uIHVzaW5nIGlzb2NyYXRpYyBlbHV0aW9uICgyMDAwIG1MIG9mIDk4OjIgaGV4YW5lczpFdE9BYyksIGFuZCBjb2xsZWN0ZWQgaW4gMjAtbUwgZnJhY3Rpb25zLg0NDQoNDQ0KRnJhY3Rpb25zIDM4LTg1IHdlcmUgY29sbGVjdGVkLCBjb21iaW5lZCwgYW5kIGNvbmNlbnRyYXRlZCB1bmRlciByZWR1Y2VkIHByZXNzdXJlIHRvIG9idGFpbiB0aGUgZmluYWwgcHJvZHVjdC4NDQ0KDQ0NClRoZSBjaGVja2VycyBmb3VuZCB0aGF0IGV4Y2VzcyBkaXRoaWFuZSBjb21wbGljYXRlZCBpc29sYXRpb24gb2YgdGhlIHByb2R1Y3QuDQ0NCg0NDQpIb3dldmVyLCBtb3N0IG9mIHRoZSBleGNlc3MgZGl0aGlhbmUgY291bGQgYmUgZWFzaWx5IHJlbW92ZWQgYnkgcGxhY2luZyB0aGUgdW5wdXJpZmllZCByZWFjdGlvbiBwcm9kdWN0IHVuZGVyIGhpZ2ggdmFjdXVtIG92ZXJuaWdodC4NDQ0KDQ0NClRoZSBjaGVja2VycyB3ZXJlIHRoZW4gYWJsZSB0byBpc29sYXRlIHRoZSBwcm9kdWN0IHVzaW5nIDM2MCBnIG9mIHNpbGljYSBhbmQgMy41IEwgb2YgOTU6NSBoZXhhbmVzOkV0T0FjLg0NDQoNDQ0KRnJhY3Rpb25zIG9mIDI1IG1MIHdlcmUgY29sbGVjdGVkLCBhbmQgdGhlIHByb2R1Y3Qgd2FzIGZvdW5kIGluIGZyYWN0aW9ucyA1NS05My48L0RJVj4NDQ0KDQ0NCjxESVYgY2xhc3M9Im5vdGVwYXJhIj48QSBuYW1lPSJub3RlMTkiIGlkPSJub3RlMTkiPjwvQT4xOS4NDQ0KCVRoZSBjaGVja2VycyBvYnNlcnZlZCB0aGF0IHlpZWxkcyB3ZXJlIGltcHJvdmVkIHN1YnN0YW50aWFsbHkgdXNpbmcgZnJlc2hseSBkaXN0aWxsZWQgZGl0aGlhbmUgKDU1ICYjMTc2O0MsIDEgbW1IZyksIHJlY2VudGx5IGNocm9tYXRvZ3JhcGhlZCB0cmlmbGF0ZSB0aGF0IHdhcyBjb25jZW50cmF0ZWQgZnJvbSBhbmh5ZHJvdXMgVEhGLCBhbmQgYSBuZXdseSBvcGVuZWQgYm90dGxlIG9mIGJ1dHlsbGl0aGl1bSBpbiBoZXhhbmVzLjwvRElWPg0NDQoNDQ0KPERJViBjbGFzcz0ibm90ZXBhcmEiPjxBIG5hbWU9Im5vdGUyMCIgaWQ9Im5vdGUyMCI+PC9BPjIwLg0NDQoJVGhlIGNvbXBvdW5kIGV4aGliaXRlZCB0aGUgZm9sbG93aW5nIHBoeXNpY2FsIGFuZCBzcGVjdHJvc2NvcGljIGRhdGE6IElSIChuZWF0KTogMjkxOCwgMTcwMCwgMTQ0NiwgMTQyMywgMTM3MiwgMTM1OSwgMTI3NywgMTI0MywgMTIxNywgMTE0OSwgMTA3MSwgOTk4LCA5MDcsIDg2OCwgNjczIGNtPHN1cD4tMTwvc3VwPi4NDQ0KDQ0NCjxzdXA+MTwvc3VwPkggTk1SIDxBIENMQVNTPSJwZGZsaW5rIiB0YXJnZXQ9Il9ibGFuayIgaHJlZj0iL2NvbnRlbnQvcGRmcy9TcGVjdHJ1bS92ODhwMDM1M19IX25vdGUyMC5wZGYiPnBkZjwvQT4oNDAwIE1IeiwgQ0RDbDxzdWI+Mzwvc3ViPikgJiM5NDg7OiAxLjY4IChzLCAzIEgpLCAxLjg3IC0gMS43MSAobSwgNiBIKSwgMi4xNCAtIDIuMDQgKG0sIDEgSCksIDIuMTggKHRkLCA8aT5KPC9pPiA9IDYuOCwgMi42IEh6LCAyIEgpLCAyLjYyIChkdCwgPGk+SjwvaT4gPSA3LjUsIDMuNSBIeiwgMiBIKSwgMi43OSAodCwgPGk+SjwvaT4gPSA3LjIgSHosIDIgSCksIDMuMTAgKHQsIDxpPko8L2k+ID0gMTMuNyBIeiwgMiBIKTsgPHN1cD4xMzwvc3VwPkMgTk1SIDxBIENMQVNTPSJwZGZsaW5rIiB0YXJnZXQ9Il9ibGFuayIgaHJlZj0iL2NvbnRlbnQvcGRmcy9TcGVjdHJ1bS92ODhwMDM1M19DX25vdGUyMC5wZGYiPnBkZjwvQT4oMTI2IE1IeiwgQ0RDbDxzdWI+Mzwvc3ViPikgJiM5NDg7OiAzLjYsIDE4LjIsIDI0LjEsIDI0LjMsIDI1LjAsIDI4LjIsIDM0LjYsIDU0LjgsIDc2LjUsIDc4LjMsIDIwMy45Lg0NDQoNDQ0KSFJNUyAoRVNJKSBjYWxjZC4NDQ0KDQ0NCmZvciBDPHN1Yj4xMjwvc3ViPkg8c3ViPjE4PC9zdWI+SE9TPHN1Yj4yPC9zdWI+W00rSF06IDI0My4wODcyLg0NDQoNDQ0KRm91bmQ6IDI0My4wODczLg0NDQoNDQ0KQW5hbC4NDQ0KDQ0NCmNhbGNkLg0NDQoNDQ0KZm9yIEM8c3ViPjEyPC9zdWI+SDxzdWI+MTg8L3N1Yj5PUzxzdWI+Mjwvc3ViPjogQywgNTkuNDY7IEgsIDcuNDg7IFMsIDI2LjQ2Lg0NDQoNDQ0KRm91bmQ6IEMsIDU5LjQ4OyBILCA3LjI1OyBTLCAyNi41OS4NDQ0KDQ0NCiANDQ0KDQ0NCjxiPlNhZmV0eSBhbmQgV2FzdGUgRGlzcG9zYWwgSW5mb3JtYXRpb248L2I+DQ0NCg0NDQogDQ0NCg0NDQogQWxsIGhhemFyZG91cyBtYXRlcmlhbHMgc2hvdWxkIGJlIGhhbmRsZWQgYW5kIGRpc3Bvc2VkIG9mIGluIGFjY29yZGFuY2Ugd2l0aCAiUHJ1ZGVudCBQcmFjdGljZXMgaW4gdGhlIExhYm9yYXRvcnkiOyBOYXRpb25hbCBBY2FkZW15IFByZXNzOyBXYXNoaW5ndG9uLCBEQywgMTk5NS4NDQ0KDQ0NCjwvRElWPg0NDQoNDQ0KPC9ESVY+DQ0NCjxESVYgQ0xBU1M9InNlY3RoZWFkaW5nIj4zLiBEaXNjdXNzaW9uPC9ESVY+DQ0NCjxESVYgQ0xBU1M9ImRpc2N1c3Npb25wYXJhIj5BbGt5bmUgYnVpbGRpbmcgYmxvY2tzIG9mZmVyIG1hbnkgYWR2YW50YWdlcyBpbiBjaGVtaWNhbCBzeW50aGVzaXMgb3dpbmcgdG8gdGhlaXIgaGlnaCBlbnRoYWxwaWMgKGNoZW1pY2FsIHBvdGVudGlhbCBlbmVyZ3kpIGNvbnRlbnQgYW5kIG9ydGhvZ29uYWwgcmVhY3Rpdml0eSB3aXRoIHJlc3BlY3QgdG8gb3RoZXIgY29tbW9uIG9yZ2FuaWMgZnVuY3Rpb25hbCBncm91cHMuPFNVUD48U1BBTiBDTEFTUz0iaG90c3BvdCIgb25tb3VzZW92ZXI9InRvb2x0aXAuc2hvdyhnZXRJdGVtVGV4dCgncmVmMicpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+PEEgdGFyZ2V0PSJfc2VsZiIgaHJlZj0iZGVtby5hc3B4P3ByZXA9djg4cDAzNTMjcmVmMiI+MjwvQT48L1NQQU4+PC9TVVA+IFRoZSBhZHZlbnQgb2YgbGF0ZSB0cmFuc2l0aW9uIG1ldGFsIGNhdGFseXN0cyB0aGF0IGRpc3BsYXkgYSBwcmVmZXJlbmNlIGZvciBjb29yZGluYXRpb24gdG8gJiM5NjA7LXN5c3RlbXMgaGFzIGV4cGFuZGVkIHRoZSBzY29wZSBvZiBhbGt5bmUgcmVhY3Rpb25zIGFuZCBmdXJ0aGVyIGluY3JlYXNlZCB0aGVpciB2YWx1ZS48U1VQPjxTUEFOIENMQVNTPSJob3RzcG90IiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdyZWYzJykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij48QSB0YXJnZXQ9Il9zZWxmIiBocmVmPSJkZW1vLmFzcHg/cHJlcD12ODhwMDM1MyNyZWYzIj4zPC9BPjwvU1BBTj48L1NVUD48L0RJVj4NDQ0KDQ0NCjxESVYgQ0xBU1M9ImRpc2N1c3Npb25wYXJhIj5BcyB0aGUgc2NvcGUgb2YgYWxreW5lIHJlYWN0aW9ucyBjb250aW51ZXMgdG8gZXhwYW5kLCBzbyB0b28gZG9lcyB0aGUgZGVtYW5kIGZvciBlZmZpY2llbnQgc3ludGhldGljIG1ldGhvZHMgdGhhdCBwcm9kdWNlIGtleSBhbGt5bmUgYnVpbGRpbmcgYmxvY2tzLg0NDQoNDQ0KSG93ZXZlciwgdGhlIGVuZXJneS1yaWNoIGFsa3luZSAmIzk2MDstc3lzdGVtIGlzIG5vdCBlYXN5IHRvIGdlbmVyYXRlLg0NDQoNDQ0KRnVuY3Rpb25hbGl6ZWQgYWxreW5lcyBhcmUgdHlwaWNhbGx5IHByZXBhcmVkIHVzaW5nIG1ldGhvZHMgdGhhdCBtYWtlIHVzZSBvZiBzaW1wbGVyIGFsa3luZSBzdGFydGluZyBtYXRlcmlhbHMsIGxpa2UgYWNldHlsaWRlIGNvdXBsaW5nLg0NDQoNDQ0KQ29tbW9uIG1ldGhvZHMgZm9yIHRoZSBnZW5lcmF0aW9uIG9mIGFsa3luZSAmIzk2MDstYm9uZHMgZnJvbSBub24tYWNldHlsZW5pYyBzdGFydGluZyBtYXRlcmlhbHMgaW5jbHVkZSBlbGltaW5hdGlvbiwgdmlueWxpZGVuZSBjYXJiZW5lIHJlYXJyYW5nZW1lbnQsIGFuZCBmcmFnbWVudGF0aW9uIHJlYWN0aW9ucy48U1VQPjxTUEFOIENMQVNTPSJob3RzcG90IiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdyZWY0JykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij48QSB0YXJnZXQ9Il9zZWxmIiBocmVmPSJkZW1vLmFzcHg/cHJlcD12ODhwMDM1MyNyZWY0Ij40PC9BPjwvU1BBTj48L1NVUD48L0RJVj4NDQ0KDQ0NCjxESVYgQ0xBU1M9ImRpc2N1c3Npb25wYXJhIj5WaW55bG9nb3VzIGFjeWwgdHJpZmxhdGVzIChWQVRzKSB1bmRlcmdvIHRhbmRlbSBudWNsZW9waGlsaWMgYWRkaXRpb24gLyBmcmFnbWVudGF0aW9uIHJlYWN0aW9ucyB0byBwcm92aWRlIHRldGhlcmVkIGtldG8tYWxreW5lcy48U1VQPjxTUEFOIENMQVNTPSJob3RzcG90IiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdyZWY1JykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij48QSB0YXJnZXQ9Il9zZWxmIiBocmVmPSJkZW1vLmFzcHg/cHJlcD12ODhwMDM1MyNyZWY1Ij41PC9BPjwvU1BBTj48L1NVUD4gVGhlIG92ZXJhbGwgc2VxdWVuY2UgYWNoaWV2ZXMgdGhlIGNvbnZlcnNpb24gb2Ygc3ltbWV0cmljLCBjeWNsaWMgZGlvbmVzIGludG8gYWN5Y2xpYyBhbGt5bnlsIGtldG9uZXMgdGhhdCBjb21wcmlzZSBvcnRob2dvbmFsIGFuZCBub24tY29udGlndW91cyBmdW5jdGlvbmFsaXRpZXMuDQ0NCg0NDQpUaGUgc3RhYmlsaXR5IG9mIHRoZSB0cmlmbGF0ZSBhbmlvbiAoYW4gZXhjZWxsZW50IGxlYXZpbmcgZ3JvdXApIGVuYWJsZXMgdGhlIGZyYWdtZW50YXRpb24gcHJvY2VzcyBpbiBtdWNoIHRoZSBzYW1lIHdheSBhcyBmb3JtYXRpb24gb2YgbW9sZWN1bGFyIG5pdHJvZ2VuIGlzIGEgZHJpdmluZyBmb3JjZSBpbiB0aGUgY2xhc3NpYyBFc2NoZW5tb3Nlci1UYW5hYmUgcmVhY3Rpb24uPFNVUD48U1BBTiBDTEFTUz0iaG90c3BvdCIgb25tb3VzZW92ZXI9InRvb2x0aXAuc2hvdyhnZXRJdGVtVGV4dCgncmVmNicpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+PEEgdGFyZ2V0PSJfc2VsZiIgaHJlZj0iZGVtby5hc3B4P3ByZXA9djg4cDAzNTMjcmVmNiI+NjwvQT48L1NQQU4+PC9TVVA+IFRoZXNlIG1lY2hhbmlzdGljYWxseSByZWxhdGVkIHJlYWN0aW9ucyBhcmUgYW1vbmcgdGhlIGZldyBDLUMgYm9uZCBjbGVhdmluZyBmcmFnbWVudGF0aW9ucyB0aGF0IHByb2R1Y2UgYWxreW5lICYjOTYwOy1zeXN0ZW1zLjxTVVA+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ3JlZjcnKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiPjxBIHRhcmdldD0iX3NlbGYiIGhyZWY9ImRlbW8uYXNweD9wcmVwPXY4OHAwMzUzI3JlZjciPjc8L0E+PC9TUEFOPjwvU1VQPjwvRElWPg0NDQoNDQ0KPERJViBDTEFTUz0iZGlzY3Vzc2lvbnBhcmEiPg0NDQo8RElWIENMQVNTPSJmaWdjYXB0aW9uIj48Yj5TY2hlbWUgMS48L2I+IEFsdGVybmF0aXZlIHN0cmF0ZWdpZXMgZm9yIHRoZSBzeW50aGVzaXMgb2YgKDxpPlo8L2k+KS02LWhlbmVpY29zZW4tMTEtb25lPC9ESVY+DQ0NCjxESVYgU1RZTEU9InRleHQtYWxpZ246Y2VudGVyO21hcmdpbjoxZW0iPjxJTUcgc3JjPSIvY29udGVudC9maWd1cmVzL3Y4OHAwMzUzLTIuZ2lmIiBhbGlnbj0ibWlkZGxlIiBhbHQ9IlNjaGVtZSAxLiBBbHRlcm5hdGl2ZSBzdHJhdGVnaWVzIGZvciB0aGUgc3ludGhlc2lzIG9mIChaKS02LWhlbmVpY29zZW4tMTEtb25lIj48L0RJVj4NDQ0KPC9ESVY+DQ0NCg0NDQo8RElWIENMQVNTPSJkaXNjdXNzaW9ucGFyYSI+VGhlIHV0aWxpdHkgb2YgY2FyYmFuaW9uLXRyaWdnZXJlZCBmcmFnbWVudGF0aW9uIG9mIHZpbnlsb2dvdXMgYWN5bCB0cmlmbGF0ZXMgYXMgYSBtb2Rlcm4gYWx0ZXJuYXRpdmUgdG8gdGhlIEVzY2hlbm1vc2VyLVRhbmFiZSBmcmFnbWVudGF0aW9uIGlzIGlsbHVzdHJhdGVkIGluIHRoZSBzeW50aGVzaXMgb2YgKDxpPlo8L2k+KS02LWhlbmVpY29zZW4tMTEtb25lLCB0aGUgc2V4IHBoZXJvbW9uZSBvZiB0aGUgRG91Z2xhcyBmaXIgdHVzc29jayBtb3RoIChGaWd1cmUgMSkuDQ0NCg0NDQpJbiBhbiBlYXJsaWVyIGFwcHJvYWNoLDxTVVA+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ3JlZjgnKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiPjxBIHRhcmdldD0iX3NlbGYiIGhyZWY9ImRlbW8uYXNweD9wcmVwPXY4OHAwMzUzI3JlZjgiPjg8L0E+PC9TUEFOPjwvU1VQPiBhIGN5Y2xpYyB2aW55bG9nb3VzIG1ldGh5bCBlc3RlciB3YXMgdHJlYXRlZCB3aXRoIDxpPm48L2k+LWRlY3lsIEdyaWduYXJkIGluIGFuIGFkZGl0aW9uLWh5ZHJvbHlzaXMgc2VxdWVuY2UgdG8gc2V0IHVwIHRoZSBtdWx0aS1zdGFnZSBFc2NoZW5tb3Nlci1UYW5hYmUgcHJvY2Vzcy4NDQ0KDQ0NClVzaW5nIHRoZSBjdXJyZW50IG1ldGhvZCwgbnVjbGVvcGhpbGljIGFkZGl0aW9uIG9mIHRoZSBzYW1lIEdyaWduYXJkIHJlYWdlbnQgdG8gdGhlIGNvcnJlc3BvbmRpbmcgdmlueWxvZ291cyB0cmlmbGF0ZSB0cmlnZ2VyZWQgZnJhZ21lbnRhdGlvbiBkaXJlY3RseS48U1VQPjxTUEFOIENMQVNTPSJob3RzcG90IiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdyZWY5JykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij48QSB0YXJnZXQ9Il9zZWxmIiBocmVmPSJkZW1vLmFzcHg/cHJlcD12ODhwMDM1MyNyZWY5Ij45PC9BPjwvU1BBTj48L1NVUD4gVGhlIHN0cmVhbWxpbmVkIGVudHJ5IGludG8gdGhlIGZyYWdtZW50YXRpb24gcGF0aHdheSBwcm92aWRlcyBhbiBpbmNyZWFzZWQgb3ZlcmFsbCB5aWVsZCBpbiBmZXdlciBzdGVwcywgYW5kIGl0IGF2b2lkcyBhY2lkaWMgY29uZGl0aW9ucyBhbmQgdGhlIHNvbWV0aW1lcy10cm91Ymxlc29tZSBwcmVwYXJhdGlvbiBvZiBjeWNsaWMgZW5vbmUgb3hpZGVzLjxTVVA+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ3JlZjYnKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiPjxBIHRhcmdldD0iX3NlbGYiIGhyZWY9ImRlbW8uYXNweD9wcmVwPXY4OHAwMzUzI3JlZjYiPjZiPC9BPjwvU1BBTj48L1NVUD48L0RJVj4NDQ0KDQ0NCjxESVYgQ0xBU1M9ImRpc2N1c3Npb25wYXJhIj5UaGUgc2NvcGUgb2YgYXBwcm9wcmlhdGUgbnVjbGVvcGhpbGVzIGlzIGlsbHVzdHJhdGVkIGluIFRhYmxlIDEuDQ0NCg0NDQpDYXJiYW5pb24gcmVhZ2VudHMgd2VyZSB0aGUgZmlyc3QgbnVjbGVvcGhpbGVzIHRvIGJlIGV4cGxvcmVkLDxTVVA+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ3JlZjUnKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiPjxBIHRhcmdldD0iX3NlbGYiIGhyZWY9ImRlbW8uYXNweD9wcmVwPXY4OHAwMzUzI3JlZjUiPjU8L0E+PC9TUEFOPjwvU1VQPiBhcyB0aGVzZSBwcm92aWRlIGFsa3lsIGFuZCBhcnlsIGtldG9uZXMgb2YgdGhlIHR5cGUgbW9zdCBjbG9zZWx5IGFzc29jaWF0ZWQgd2l0aCB0aGUgRXNjaGVubW9zZXItVGFuYWJlIGZyYWdtZW50YXRpb24gKGVudHJpZXMgMS00LCAxMC0xMikuDQ0NCg0NDQpUaGUgdHlwaWNhbCByZWFjdGlvbiBpcyBjb25kdWN0ZWQgYnkgdHJlYXRpbmcgdGhlIG51Y2xlb3BoaWxlIHdpdGggdGhlIHZpbnlsb2dvdXMgYWN5bCB0cmlmbGF0ZSBpbiBUSEYgYXQgbG93IHRlbXBlcmF0dXJlIHRvIGFjaGlldmUgdGhlIGluaXRpYWwgMSwyLWFkZGl0aW9uLCBhbmQgdGhlbiB3YXJtaW5nIHRoZSByZWFjdGlvbiBtaXh0dXJlIHRvIHJvb20gdGVtcGVyYXR1cmUgb3IgYWJvdmUgdG8gcHJvbW90ZSB0aGUgKGVudHJvcGljYWxseSBmYXZvcmFibGUpIGZyYWdtZW50YXRpb24gZXZlbnQuDQ0NCg0NDQpJdCBoYXMgYmVlbiBvYnNlcnZlZCBleHBlcmltZW50YWxseSB0aGF0IGFkZGl0aW9uIC8gZnJhZ21lbnRhdGlvbiByZWFjdGlvbnMgdXNpbmcgdW5zdGFiaWxpemVkDQ0NCg0NDQo8L0RJVj4NDQ0KDQ0NCjxESVYgQ0xBU1M9ImRpc2N1c3Npb25wYXJhIj4NDQ0KPERJViBDTEFTUz0iZmlnY2FwdGlvbiI+PGI+VGFibGUgMS48L2I+IFNjb3BlIG9mIHRoZSBhZGRpdGlvbi9mcmFnbWVudGF0aW9uIHJlYWN0aW9uPC9ESVY+DQ0NCjxESVYgU1RZTEU9InRleHQtYWxpZ246Y2VudGVyO21hcmdpbjoxZW0iPjxJTUcgc3JjPSIvY29udGVudC9maWd1cmVzL3Y4OHAwMzUzLTMuZ2lmIiBhbGlnbj0ibWlkZGxlIiBhbHQ9IlRhYmxlIDEuIFNjb3BlIG9mIHRoZSBhZGRpdGlvbi9mcmFnbWVudGF0aW9uIHJlYWN0aW9uIj48L0RJVj4NDQ0KPC9ESVY+DQ0NCg0NDQo8RElWIENMQVNTPSJkaXNjdXNzaW9ucGFyYSI+YWxreWxsaXRoaXVtIGFuZCBhbGt5bCBHcmlnbmFyZCByZWFnZW50cyBvY2N1ciBtb3JlIGVmZmljaWVudGx5IGluIHRvbHVlbmUgdGhhbiBpbiBUSEYgKGVudHJ5IDIpOzxTVVA+PFNQQU4gQ0xBU1M9ImhvdHNwb3QiIG9ubW91c2VvdmVyPSJ0b29sdGlwLnNob3coZ2V0SXRlbVRleHQoJ3JlZjknKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiPjxBIHRhcmdldD0iX3NlbGYiIGhyZWY9ImRlbW8uYXNweD9wcmVwPXY4OHAwMzUzI3JlZjkiPjk8L0E+PC9TUEFOPjwvU1VQPiB0aGlzIG9ic2VydmF0aW9uIG1heSBiZSBhdHRyaWJ1dGFibGUgdG8gc29sdmVudC1kZXBlbmRlbnQgYWdncmVnYXRpb24gc3RhdGVzIG9mIHRoZSBvcmdhbm9tZXRhbGxpYyByZWFnZW50Lg0NDQoNDQ0KSW4gdG9sdWVuZSwgaGlnaGVyIGFnZ3JlZ2F0aW9uIHN0YXRlcyBvZiB0aGUgbnVjbGVvcGhpbGUgbGlrZWx5IGF0dGVudWF0ZSBpdHMgcmVhY3Rpdml0eSBhbmQgcHJvbW90ZSBzZWxlY3Rpdml0eSBmb3IgdGhlIGRlc2lyZWQgMSwyLWFkZGl0aW9uIG92ZXIgYWx0ZXJuYXRpdmUgcGF0aHdheXMgbGlrZSBwcm90b24tIG9yIGVsZWN0cm9uLXRyYW5zZmVyLjwvRElWPg0NDQoNDQ0KPERJViBDTEFTUz0iZGlzY3Vzc2lvbnBhcmEiPkFkZGl0aW9uIG9mIHN0YWJpbGl6ZWQgY2FyYmFuaW9uIG51Y2xlb3BoaWxlcyB0byB2aW55bG9nb3VzIGFjeWwgdHJpZmxhdGVzIHRyaWdnZXJzIHdoYXQgd2UgdGVybSB0aGUgVkFULUNsYWlzZW48U1VQPjxTUEFOIENMQVNTPSJob3RzcG90IiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdyZWYxMCcpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+PEEgdGFyZ2V0PSJfc2VsZiIgaHJlZj0iZGVtby5hc3B4P3ByZXA9djg4cDAzNTMjcmVmMTAiPjEwPC9BPjwvU1BBTj48L1NVUD4gcmVhY3Rpb246IGEgcmluZy1vcGVuaW5nIGZyYWdtZW50YXRpb24gdG8gZ2l2ZSBhY3ljbGljICYjOTQ2Oy1rZXRvIGVzdGVyIGFuZCByZWxhdGVkIHByb2R1Y3RzIG11Y2ggbGlrZSB0aG9zZSBvYnNlcnZlZCB0cmFkaXRpb25hbGx5IGluIHRoZSBDbGFpc2VuIGNvbmRlbnNhdGlvbiAoZW50cmllcyA1LTYpLg0NDQoNDQ0KV2hlcmVhcyB0aGUgQ2xhaXNlbiBjb25kZW5zYXRpb24gaXMgZHJpdmVuIGJ5IGRlcHJvdG9uYXRpb24gb2YgZmluYWwgcHJvZHVjdCwgdGhlIFZBVC1DbGFpc2VuIHJlYWN0aW9uIGlzIHJlbmRlcmVkIGlycmV2ZXJzaWJsZSBieSB0aGUgZnJhZ21lbnRhdGlvbiBldmVudC4NDQ0KDQ0NCkRlcHJvdG9uYXRpb24gb2YgdGhlIGZpbmFsIFZBVC1DbGFpc2VuIHByb2R1Y3QgbWF5IHN0aWxsIG9jY3VyIGluY2lkZW50YWxseSwgaW4gd2hpY2ggY2FzZSB0aGUgdXNlIG9mIGV4Y2VzcyBudWNsZW9waGlsZSBpcyByZXF1aXJlZCB0byByZWFsaXplIGNvbXBsZXRlIGNvbnZlcnNpb24gKGVudHJ5IDUpLjwvRElWPg0NDQoNDQ0KPERJViBDTEFTUz0iZGlzY3Vzc2lvbnBhcmEiPk90aGVyIHN1aXRhYmxlIG51Y2xlb3BoaWxlcyBmb3IgcHJvbW90aW5nIGZyYWdtZW50YXRpb24gaW5jbHVkZSBwcmltYXJ5IGxpdGhpdW0gYW1pZGVzIChlbnRyeSA3KSBhbmQgbGl0aGl1bSB0cmlldGh5bGJvcm9oeWRyaWRlIChlbnRyeSA4KS48U1VQPjxTUEFOIENMQVNTPSJob3RzcG90IiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdyZWY1JykpOyIgb25tb3VzZW91dD0idG9vbHRpcC5oaWRlKCk7Ij48QSB0YXJnZXQ9Il9zZWxmIiBocmVmPSJkZW1vLmFzcHg/cHJlcD12ODhwMDM1MyNyZWY1Ij41PC9BPjwvU1BBTj48L1NVUD4gRGlpc29idXR5bGFsdW1pbnVtIGh5ZHJpZGUgcmVkdWNlcyB0aGUgVkFUIGNhcmJvbnlsIGJ1dCBkb2VzIG5vdCB0cmlnZ2VyIGZyYWdtZW50YXRpb247IHRoZSByZXN1bHRpbmcgYWxjb2hvbCBjYW4gdGhlbiBiZSB0cmVhdGVkIHdpdGggZXhjZXNzIEdyaWduYXJkIHJlYWdlbnRzIHRvIHByb21vdGUgZnJhZ21lbnRhdGlvbiBhbmQgaW4gc2l0dSB0cmFwcGluZyBvZiB0aGUgcmVzdWx0YW50IGFsZGVoeWRlIChlbnRyeSA5KS48U1VQPjxTUEFOIENMQVNTPSJob3RzcG90IiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdyZWYxMScpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+PEEgdGFyZ2V0PSJfc2VsZiIgaHJlZj0iZGVtby5hc3B4P3ByZXA9djg4cDAzNTMjcmVmMTEiPjExPC9BPjwvU1BBTj48L1NVUD4gT3RoZXIgc3VpdGFibGUgVkFUIHN1YnN0cmF0ZXMgYXJlIHNob3duIGluIGVudHJpZXMgMTAtMTIuDQ0NCg0NDQpUaGUgZml2ZS0gYW5kIHNldmVuLW1lbWJlcmVkIHJpbmcgVkFUcyBhcmUgbGVzcyBzdGFibGUgdGhhbiB0aGVpciBoZXhhY3ljbGljIGNvdW50ZXJwYXJ0cywgYW5kIGFzIHN1Y2ggdGhleSBhcmUgYmVzdCBwcmVwYXJlZCBpbW1lZGlhdGVseSBwcmlvciB0byB1c2UuPC9ESVY+DQ0NCg0NDQo8RElWIENMQVNTPSJkaXNjdXNzaW9ucGFyYSI+VGhlIHRhbmRlbSBudWNsZW9waGlsaWMgYWRkaXRpb24gLyBmcmFnbWVudGF0aW9uIG9mIGN5Y2xpYyBWQVQgc3Vic3RyYXRlcyBwcm92aWRlcyBhbiBhbHRlcm5hdGl2ZSBlbnRyeSBpbnRvIHRoZSBjbGFzc2ljIEVzY2hlbm1vc2VyLVRhbmFiZSBwYXRod2F5LCBvbmUgb2YgdGhlIGZldyBHcm9iLXR5cGUgZnJhZ21lbnRhdGlvbnMgY2FwYWJsZSBvZiBnZW5lcmF0aW5nIGFsa3luZSAmIzk2MDstYm9uZHMuDQ0NCg0NDQpUaGUgbWV0aG9kIG91dGxpbmVkIGFib3ZlIGRlbGl2ZXJzIG9ydGhvZ29uYWxseSBmdW5jdGlvbmFsaXplZCBhY3ljbGljIGJ1aWxkaW5nIGJsb2NrcyAtIGFsa3lueWwga2V0b25lcyBhbmQgcmVsYXRlZCBjb21wb3VuZHMgLSBmcm9tIHN5bW1ldHJpY2FsIGN5Y2xpYyBkaW9uZSBzdGFydGluZyBtYXRlcmlhbHMuDQ0NCg0NDQpUaGlzIG1ldGhvZG9sb2d5IGNvbnRpbnVlcyB0byBldm9sdmU7IGFwcGxpY2F0aW9uIHRvIHRoZSBzeW50aGVzaXMgb2YgbmF0dXJhbCBwcm9kdWN0cyw8U1VQPjxTUEFOIENMQVNTPSJob3RzcG90IiBvbm1vdXNlb3Zlcj0idG9vbHRpcC5zaG93KGdldEl0ZW1UZXh0KCdyZWYxMicpKTsiIG9ubW91c2VvdXQ9InRvb2x0aXAuaGlkZSgpOyI+PEEgdGFyZ2V0PSJfc2VsZiIgaHJlZj0iZGVtby5hc3B4P3ByZXA9djg4cDAzNTMjcmVmMTIiPjEyPC9BPjwvU1BBTj48L1NVUD4gaG9tb3Byb3Bhcmd5bCBhbGNvaG9sPFNVUD48U1BBTiBDTEFTUz0iaG90c3BvdCIgb25tb3VzZW92ZXI9InRvb2x0aXAuc2hvdyhnZXRJdGVtVGV4dCgncmVmMTMnKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiPjxBIHRhcmdldD0iX3NlbGYiIGhyZWY9ImRlbW8uYXNweD9wcmVwPXY4OHAwMzUzI3JlZjEzIj4xMzwvQT48L1NQQU4+PC9TVVA+IGFuZCBob21vcHJvcGFyZ3lsIGFtaW5lPFNVUD48U1BBTiBDTEFTUz0iaG90c3BvdCIgb25tb3VzZW92ZXI9InRvb2x0aXAuc2hvdyhnZXRJdGVtVGV4dCgncmVmMTQnKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiPjxBIHRhcmdldD0iX3NlbGYiIGhyZWY9ImRlbW8uYXNweD9wcmVwPXY4OHAwMzUzI3JlZjE0Ij4xNDwvQT48L1NQQU4+PC9TVVA+IGRlcml2YXRpdmVzIGZyb20gaGV0ZXJvY3ljbGljIFZBVHMsIGFuZCBvdGhlciBjaGFsbGVuZ2luZyBjbGFzc2VzIG9mIG9yZ2FuaWMgY29tcG91bmRzPFNVUD48U1BBTiBDTEFTUz0iaG90c3BvdCIgb25tb3VzZW92ZXI9InRvb2x0aXAuc2hvdyhnZXRJdGVtVGV4dCgncmVmMTUnKSk7IiBvbm1vdXNlb3V0PSJ0b29sdGlwLmhpZGUoKTsiPjxBIHRhcmdldD0iX3NlbGYiIGhyZWY9ImRlbW8uYXNweD9wcmVwPXY4OHAwMzUzI3JlZjE1Ij4xNTwvQT48L1NQQU4+PC9TVVA+IGFyZSB1bmRlcndheSBhdCB0aGlzIHRpbWUuPC9ESVY+DQ0NCg0NDQo8SFI+DQ0NCjxESVYgQ0xBU1M9ImZvb3Rub3RlcyI+DQ0NCjxESVYgQ0xBU1M9ImZvb3Rub3RlaGVhZCI+UmVmZXJlbmNlcyBhbmQgTm90ZXM8L0RJVj4NDQ0KPE9MIENMQVNTPSJmb290bm90ZWxpc3QiPg0NDQo8TEkgQ0xBU1M9ImZvb3Rub3RlaXRlbSI+PFNQQU4gQ0xBU1M9ImZvb3Rub3RlY29udGVudCI+PEEgbmFtZT0icmVmMSIgaWQ9InJlZjEiPjwvQT5EZXBhcnRtZW50IG9mIENoZW1pc3RyeSBhbmQgQmlvY2hlbWlzdHJ5LCBGbG9yaWRhIFN0YXRlIFVuaXZlcnNpdHksIFRhbGxhaGFzc2VlLCBGTCAzMjMwNi00MzkwLCBVU0EuIEUtTWFpbDogZ2R1ZGxleUBjaGVtLmZzdS5lZHUgVGhpcyB3b3JrIHdhcyBzdXBwb3J0ZWQgYnkgYSBncmFudCBmcm9tIHRoZSBOYXRpb25hbCBTY2llbmNlIEZvdW5kYXRpb24gKE5TRi1DSEUgMDc0OTkxOCkuIE0uUC5MLiBpcyBhIHJlY2lwaWVudCBvZiB0aGUgQ2FwZXMtRnVsYnJpZ2h0IEdyYWR1YXRlIFJlc2VhcmNoIEZlbGxvd3NoaXAgKDIwMDgpLiBULlQuSC4gaXMgYSByZWNpcGllbnQgb2YgdGhlIFZpZXRuYW0gRWR1Y2F0aW9uIEZvdW5kYXRpb24gKFZFRikgR3JhZHVhdGUgRmVsbG93c2hpcCAoMjAwOSkuPC9TUEFOPjwvTEk+DQ0NCjxMSSBDTEFTUz0iZm9vdG5vdGVpdGVtIj48U1BBTiBDTEFTUz0iZm9vdG5vdGVjb250ZW50Ij48QSBuYW1lPSJyZWYyIiBpZD0icmVmMiI+PC9BPkFsbC1DYXJib24gRnVuY3Rpb25zIFBvbHl5bmVzLCBBcnluZXMsIEVueW5lcywgYW5kIEFsa3luZXMuIEluIDxpPlNjaWVuY2Ugb2YgU3ludGhlc2lzOiBIb3ViZW4tV2V5bCBNZXRob2RzIG9mIE1vbGVjdWxhciBUcmFuc2Zvcm1hdGlvbjs8L2k+IFRob21hcywgRS4gSi4sIEhvcGYsIEguLCBFZHMuLCBUaGllbWU6IFN0dXR0Z2FydCwgMjAwODsgVm9sLiA0My48L1NQQU4+PC9MST4NDQ0KPExJIENMQVNTPSJmb290bm90ZWl0ZW0iPjxTUEFOIENMQVNTPSJmb290bm90ZWNvbnRlbnQiPjxBIG5hbWU9InJlZjMiIGlkPSJyZWYzIj48L0E+KGEpIFRzdWppLCBKLiA8aT5UcmFuc2l0aW9uIE1ldGFsIFJlYWdlbnRzIGFuZCBDYXRhbHlzdHM6IElubm92YXRpb25zIGluIE9yZ2FuaWMgU3ludGhlc2lzPC9pPjsgV2lsZXkgJmFtcDsgU29uczogTmV3IFlvcmssIDIwMDAuIChiKSA8aT5MZXdpcyBBY2lkcyBpbiBPcmdhbmljIFN5bnRoZXNpczsgWWFtYW1vdG88L2k+LCBILiwgRWQuOyBXaWxleS1WQ0g6IE5ldyBZb3JrLCAyMDAwLjwvU1BBTj48L0xJPg0NDQo8TEkgQ0xBU1M9ImZvb3Rub3RlaXRlbSI+PFNQQU4gQ0xBU1M9ImZvb3Rub3RlY29udGVudCI+PEEgbmFtZT0icmVmNCIgaWQ9InJlZjQiPjwvQT4oYSkgTGFyb2NrLCBSLiBDLiA8aT5Db21wcmVoZW5zaXZlIE9yZ2FuaWMgVHJhbnNmb3JtYXRpb25zLDwvaT4gMm5kIEVkLjsgV2lsZXkgJmFtcDsgU29uczogTmV3IFlvcmssIDE5OTk7IHBwIDU2My01ODMuIChiKSBCcmFuZHNtYSwgTC4gUHJlcGFyYXRpdmUgQWNldHlsZW5pYyBDaGVtaXN0cnksIDJuZCBFZC47IEVsc2V2aWVyOiBBbXN0ZXJkYW0sIDE5ODguPC9TUEFOPjwvTEk+DQ0NCjxMSSBDTEFTUz0iZm9vdG5vdGVpdGVtIj48U1BBTiBDTEFTUz0iZm9vdG5vdGVjb250ZW50Ij48QSBuYW1lPSJyZWY1IiBpZD0icmVmNSI+PC9BPihhKSBLYW1pam8sIFMuOyBEdWRsZXksIEcuIEIuIDxpPkouIEFtLiBDaGVtLiBTb2MuPC9pPiA8Yj4yMDA1PC9iPiwgPGk+MTI3PC9pPiwgNTAyOC01MDI5LiAoYikgS2FtaWpvLCBTLjsgRHVkbGV5LCBHLiBCLiA8aT5KLiBBbS4gQ2hlbS4gU29jLjwvaT4gPGI+MjAwNjwvYj4sIDxpPjEyODwvaT4sIDY0OTktNjUwNzsgQWRkaXRpb24vQ29ycmVjdGlvbjogPGk+Si4gQW0uIENoZW0uIFNvYy48L2k+IDxiPjIwMTA8L2I+LCA8aT4xMzI8L2k+LCA4MjIzLjwvU1BBTj48L0xJPg0NDQo8TEkgQ0xBU1M9ImZvb3Rub3RlaXRlbSI+PFNQQU4gQ0xBU1M9ImZvb3Rub3RlY29udGVudCI+PEEgbmFtZT0icmVmNiIgaWQ9InJlZjYiPjwvQT4oYSkgRXNjaGVubW9zZXIsIEEuOyBGZWxpeCwgRC47IE9obG9mZiwgRy4gPGk+SGVsdi4gQ2hpbS4gQWN0YTwvaT4gPGI+MTk2NzwvYj4sIDxpPjUwPC9pPiwgNzA4LTcxMy4gKGIpIFRhbmFiZSwgTS47IENyb3dlLCBELiBGLjsgRGVobiwgUi4gTC4gPGk+VGV0cmFoZWRyb24gTGV0dC48L2k+IDxiPjE5Njc8L2I+LCAzOTQzLTM5NDYuIChjKSBHcm9iLCBDLiBBLjsgU2NoaWVzcywgUC4gVy4gSC4gPGk+QW5nZXcuIENoZW0uLCBJbnQuIEVkLiBFbmdsLjwvaT4gPGI+MTk2NzwvYj4sIDxpPjY8L2k+LCAxLTE1LiAoZCkgV2V5ZXJzdGFobCwgUC47IE1hcnNjaGFsbCwgSC4gSW4gPGk+Q29tcHJlaGVuc2l2ZSBPcmdhbmljIFN5bnRoZXNpczwvaT4sIFRyb3N0LCBCLiBNLiwgRmxlbWluZywgSS4sIEVkcy47IFBlcmdhbW9uIFByZXNzOiBFbG1zZm9yZCwgTlksIDE5OTE7IFZvbC4gNiwgcHAgMTA0MS0xMDcwLiAoZSkgUHJhbnR6LCBLLjsgTXVsemVyLCBKLiA8aT5DaGVtLiBSZXY8L2k+LiA8Yj4yMDEwPC9iPiwgPGk+MTEwPC9pPiwgMzc0MS0zNzY2LjwvU1BBTj48L0xJPg0NDQo8TEkgQ0xBU1M9ImZvb3Rub3RlaXRlbSI+PFNQQU4gQ0xBU1M9ImZvb3Rub3RlY29udGVudCI+PEEgbmFtZT0icmVmNyIgaWQ9InJlZjciPjwvQT4oYSkgRm9yIGFuIGVhcmx5IGV4YW1wbGUgZHJpdmVuIGJ5IGZvcm1hdGlvbiBvZiBjYXJib24gZGlveGlkZSwgc2VlOiBHcm9iLCBDLiBBLjsgQ3NhcGlsbGEsIEouIENzZWgsIEcuIDxpPkhlbHYuIENoaW0uIEFjdGE8L2k+IDxiPjE5NjQ8L2I+LCA8aT40NzwvaT4sIDE1OTAtMTYwMi4gKGIpIEZvciByZWNlbnQgZXhhbXBsZXMgZHJpdmVuIGJ5IGZvcm1hdGlvbiBvZiBtb2xlY3VsYXIgbml0cm9nZW4sIHNlZTogRHJhZ2hpY2ksIEMuOyBCcmV3ZXIsIE0uIDxpPkouIEFtLiBDaGVtLiBTb2MuPC9pPiA8Yj4yMDA4PC9iPiwgPGk+MTMwPC9pPiwgMzc2Ni0zNzY3OyAoYykgRHJhZ2hpY2ksIEMuOyBIdWFuZywgUS47IEJyZXdlciwgTS4gPGk+Si4gT3JnLiBDaGVtLjwvaT4gPGI+MjAwOTwvYj4sIDxpPjc0PC9pPiwgODQxMC04NDEzOyAoZCkgQmF5aXIsIEEuOyBEcmFnaGljaSwgQy47IEJyZXdlciwgTS4gPGk+Si4gT3JnLiBDaGVtLjwvaT4gPGI+MjAxMDwvYj4sIDxpPjc1PC9pPiwgMjk2LTMwMi48L1NQQU4+PC9MST4NDQ0KPExJIENMQVNTPSJmb290bm90ZWl0ZW0iPjxTUEFOIENMQVNTPSJmb290bm90ZWNvbnRlbnQiPjxBIG5hbWU9InJlZjgiIGlkPSJyZWY4Ij48L0E+S29jaWVuc2tpLCBQLiBKLjsgQ2VybmlnbGlhcm8sIEcuIEouIDxpPkouIE9yZy4gQ2hlbS48L2k+IDxiPjE5NzY8L2I+LCA8aT40MTwvaT4sIDI5MjctMjkyOC48L1NQQU4+PC9MST4NDQ0KPExJIENMQVNTPSJmb290bm90ZWl0ZW0iPjxTUEFOIENMQVNTPSJmb290bm90ZWNvbnRlbnQiPjxBIG5hbWU9InJlZjkiIGlkPSJyZWY5Ij48L0E+Sm9uZXMsIEQuIE0uOyBLYW1pam8sIFMuOyBEdWRsZXksIEcuIEIuIDxpPlN5bmxldHQ8L2k+IDxiPjIwMDY8L2I+LCA5MzYtOTM4LjwvU1BBTj48L0xJPg0NDQo8TEkgQ0xBU1M9ImZvb3Rub3RlaXRlbSI+PFNQQU4gQ0xBU1M9ImZvb3Rub3RlY29udGVudCI+PEEgbmFtZT0icmVmMTAiIGlkPSJyZWYxMCI+PC9BPihhKSBLYW1pam8sIFMuOyBEdWRsZXksIEcuIEIuIDxpPk9yZy4gTGV0dC48L2k+IDxiPjIwMDY8L2I+LCA8aT44LDwvaT4gMTc1LTE3Ny4gKGIpIEpvbmVzLCBELiBNLjsgTGlzYm9hLCBNLiBQLjsgS2FtaWpvLCBTLjsgRHVkbGV5LCBHLiBCLiA8aT5KLiBPcmcuIENoZW0uPC9pPiA8Yj4yMDEwPC9iPiwgPGk+NzU8L2k+LCAzMjYwLTMyNjcuPC9TUEFOPjwvTEk+DQ0NCjxMSSBDTEFTUz0iZm9vdG5vdGVpdGVtIj48U1BBTiBDTEFTUz0iZm9vdG5vdGVjb250ZW50Ij48QSBuYW1lPSJyZWYxMSIgaWQ9InJlZjExIj48L0E+S2FtaWpvLCBTLjsgRHVkbGV5LCBHLiBCLiA8aT5UZXRyYWhlZHJvbiBMZXR0LjwvaT4gPGI+MjAwNjwvYj4sIDxpPjQ3PC9pPiwgNTYyOS01NjMyLjwvU1BBTj48L0xJPg0NDQo8TEkgQ0xBU1M9ImZvb3Rub3RlaXRlbSI+PFNQQU4gQ0xBU1M9ImZvb3Rub3RlY29udGVudCI+PEEgbmFtZT0icmVmMTIiIGlkPSJyZWYxMiI+PC9BPkpvbmVzLCBELiBNLjsgRHVkbGV5LCBHLiBCLiA8aT5TeW5sZXR0PC9pPiA8Yj4yMDEwPC9iPiwgMjIzLTIyNi48L1NQQU4+PC9MST4NDQ0KPExJIENMQVNTPSJmb290bm90ZWl0ZW0iPjxTUEFOIENMQVNTPSJmb290bm90ZWNvbnRlbnQiPjxBIG5hbWU9InJlZjEzIiBpZD0icmVmMTMiPjwvQT5UdW1tYXRvcm4sIEouOyBEdWRsZXksIEcuIEIuIDxpPkouIEFtLiBDaGVtLiBTb2MuPC9pPiA8Yj4yMDA4PC9iPiwgPGk+MTMwPC9pPiwgNTA1MC01MDUxLjwvU1BBTj48L0xJPg0NDQo8TEkgQ0xBU1M9I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<div class="source"><i>Org. Synth.</i> <b>2011</b>, <i>88</i>, 353-363</div>
<div class="source">DOI: 10.15227/orgsyn.088.0353</div>
<div class="title"><span class="chemname">TANDEM NUCLEOPHILIC</span> ADDITION / FRAGMENTATION OF <span class="chemname">VINYLOGOUS ACYL TRIFLATES: 2-METHYL-2-(1-OXO-5-HEPTYNYL)-1,3-DITHIANE</span></div>
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<div class="authors"> Submitted by Marilda P. Lisboa, Tung T. Hoang, and Gregory B.
Dudley<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref1'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref1">1</a></span></sup>.</div>
<div class="authors"> Checked by Jimmie Weaver and Jonathan Ellman.</div>
<div class="authors"></div>
<div class="sectheading">1. Procedure</div>
<div class="step">
<div class="steppara"><b>Caution:</b> <i>Exercise care in the handling of trifluoromethanesulfonic anhydride (corrosive), pyridine (harmful by inhalation), and butyllithium (flammable, corrosive).</i></div>
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<div class="step">
<div class="steppara"><i>A.</i> <span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(15873));" onmouseout="tooltip.hide();"
onclick="jsShowCpdTip(15873);"><i>2-Methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one.</i></span></span></span> <i>An</i> oven-dried 2-L, three-necked, round-bottomed flask equipped with a 1 inch oval magnetic stir
bar, a rubber septum, nitrogen inlet and thermometer is charged with 2-methyl-1,3-<span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(3518));" onmouseout="tooltip.hide();"
onclick="jsShowCpdTip(3518);">cyclohexanedione</span></span> (15.0 g, 0.115 mol, 1.0 equiv)</span> <span class="hotspot" onclick="javascript:jsToolTipGoto('note1')" onmouseover="tooltip.show(getItemText('note1'));"
onmouseout="tooltip.hide();">(Note 1)</span>, <span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(270));" onmouseout="tooltip.hide();"
onclick="jsShowCpdTip(270);">pyridine</span></span> (19.0 mL, 0.230 mol, 2 equiv)</span> <span class="hotspot" onclick="javascript:jsToolTipGoto('note2')" onmouseover="tooltip.show(getItemText('note2'));"
onmouseout="tooltip.hide();">(Note 2)</span> and methylene chloride (700 mL) <span class="hotspot" onclick="javascript:jsToolTipGoto('note3')" onmouseover="tooltip.show(getItemText('note3'));"
onmouseout="tooltip.hide();">(Note 3)</span>. The reaction mixture is magnetically stirred, cooled at -78 °C for 20 min <span class="hotspot" onclick="javascript:jsToolTipGoto('note4')"
onmouseover="tooltip.show(getItemText('note4'));" onmouseout="tooltip.hide();">(Note 4)</span>, and <span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(6805));"
onmouseout="tooltip.hide();" onclick="jsShowCpdTip(6805);">trifluoromethanesulfonic anhydride</span></span> (23.5 mL, 0.138 mol, 1.2 equiv)</span> <span class="hotspot" onclick="javascript:jsToolTipGoto('note1')"
onmouseover="tooltip.show(getItemText('note1'));" onmouseout="tooltip.hide();">(Note 1)</span> is added dropwise via syringe over 10 min (Notes <span class="hotspot" onclick="javascript:jsToolTipGoto('note5')"
onmouseover="tooltip.show(getItemText('note5'));" onmouseout="tooltip.hide();">5</span> and <span class="hotspot" onclick="javascript:jsToolTipGoto('note6')" onmouseover="tooltip.show(getItemText('note6'));"
onmouseout="tooltip.hide();">6</span>). The light yellow reaction mixture is stirred at -78 °C for 20 min, at 0 °C for 20 min, and at room temperature for 30 min <span class="hotspot"
onclick="javascript:jsToolTipGoto('note4')" onmouseover="tooltip.show(getItemText('note4'));" onmouseout="tooltip.hide();">(Note 4)</span>, at which time the reaction mixture is a homogeneous red solution. The reaction mixture
is acidified using 200 mL of a 1M aqueous solution of hydrochloric acid <span class="hotspot" onclick="javascript:jsToolTipGoto('note7')" onmouseover="tooltip.show(getItemText('note7'));" onmouseout="tooltip.hide();">(Note
7)</span>, and the resulting biphasic solution is transferred to a 2-L separatory funnel. The organic phase is removed, and the aqueous layer is extracted with <span class="chemical"><span class="chemname"><span
class="hotspot" onmouseover="tooltip.show(jsLoadCpd(17));" onmouseout="tooltip.hide();" onclick="jsShowCpdTip(17);">diethyl ether</span></span> (3 x 200 mL)</span> <span class="hotspot"
onclick="javascript:jsToolTipGoto('note8')" onmouseover="tooltip.show(getItemText('note8'));" onmouseout="tooltip.hide();">(Note 8)</span>. The organic phases are combined and dried over 100 g of Na<sub>2</sub>SO<sub>4</sub>
and filtered by vacuum suction through a medium porosity fritted glass funnel, and the solvent is removed under reduced pressure by rotary evaporation (25-45 mmHg, room temperature water bath) providing the crude product as a
red oil <span class="hotspot" onclick="javascript:jsToolTipGoto('note9')" onmouseover="tooltip.show(getItemText('note9'));" onmouseout="tooltip.hide();">(Note 9)</span>. The crude product is purified by chromatography on silica
gel <span class="hotspot" onclick="javascript:jsToolTipGoto('note10')" onmouseover="tooltip.show(getItemText('note10'));" onmouseout="tooltip.hide();">(Note 10)</span> to afford 30.0 g (98%) of the product as a colorless oil
<span class="hotspot" onclick="javascript:jsToolTipGoto('note11')" onmouseover="tooltip.show(getItemText('note11'));" onmouseout="tooltip.hide();">(Note 11)</span>. 2-Methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one is
indefinitely stable to storage under nitrogen at -13 °C.</div>
</div>
<div class="step">
<div class="steppara"><i>B.</i> <span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(15874));" onmouseout="tooltip.hide();"
onclick="jsShowCpdTip(15874);"><i>2-Methyl-2-(1-oxo-5-heptynyl)-1,3-dithiane.</i></span></span></span> An oven-dried two-necked, 500-mL, round-bottomed flask equipped with 0.5 inch oval magnetic stir bar, rubber septum,
and a nitrogen inlet adapter is charged with 2-methyl-1,3-dithiane <span class="hotspot" onclick="javascript:jsToolTipGoto('note12')" onmouseover="tooltip.show(getItemText('note12'));" onmouseout="tooltip.hide();">(Note
12)</span> (4.64 mL, 38.7 mmol, 1.1 equiv) and tetrahydrofuran (150 mL) <span class="hotspot" onclick="javascript:jsToolTipGoto('note13')" onmouseover="tooltip.show(getItemText('note13'));" onmouseout="tooltip.hide();">(Note
13)</span>. The resulting solution is cooled at -78 °C <span class="hotspot" onclick="javascript:jsToolTipGoto('note4')" onmouseover="tooltip.show(getItemText('note4'));" onmouseout="tooltip.hide();">(Note 4)</span>. A
solution of <i>n</i>-butyllithium <span class="hotspot" onclick="javascript:jsToolTipGoto('note14')" onmouseover="tooltip.show(getItemText('note14'));" onmouseout="tooltip.hide();">(Note 14)</span> (14.5 mL, 35.2 mmol, 1.0
equiv) is added dropwise via syringe over 10 min <span class="hotspot" onclick="javascript:jsToolTipGoto('note15')" onmouseover="tooltip.show(getItemText('note15'));" onmouseout="tooltip.hide();">(Note 15)</span>. The light
yellow reaction mixture is stirred at -78 °C for 20 min, at 0 °C for 10 min, and at -30 °C for 15 min <span class="hotspot" onclick="javascript:jsToolTipGoto('note4')" onmouseover="tooltip.show(getItemText('note4'));"
onmouseout="tooltip.hide();">(Note 4)</span>, and then <span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(15873));" onmouseout="tooltip.hide();"
onclick="jsShowCpdTip(15873);">2-methyl-3-trifluoromethanesulfonyloxy-cyclohex-2-en-1-one</span></span> (10.0 g, 38.7 mmol, 1.1 equiv)</span> is added dropwise by syringe over 10 min. The light yellow reaction mixture is
stirred at -30 °C for 15 min, at 0 °C for 15 min, and at room temperature for 30 min <span class="hotspot" onclick="javascript:jsToolTipGoto('note4')" onmouseover="tooltip.show(getItemText('note4'));"
onmouseout="tooltip.hide();">(Note 4)</span>, at which time the reaction mixture is a homogeneous red solution <span class="hotspot" onclick="javascript:jsToolTipGoto('note16')"
onmouseover="tooltip.show(getItemText('note16'));" onmouseout="tooltip.hide();">(Note 16)</span>. A half-saturated solution of <span class="chemical"><span class="chemname">aqueous ammonium chloride</span> (100 mL)</span>
<span class="hotspot" onclick="javascript:jsToolTipGoto('note17')" onmouseover="tooltip.show(getItemText('note17'));" onmouseout="tooltip.hide();">(Note 17)</span> is then added and the biphasic solution is transferred to a
500-mL separatory funnel and extracted with <span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(17));" onmouseout="tooltip.hide();" onclick="jsShowCpdTip(17);">diethyl
ether</span></span> (3 x 50 mL)</span> <span class="hotspot" onclick="javascript:jsToolTipGoto('note8')" onmouseover="tooltip.show(getItemText('note8'));" onmouseout="tooltip.hide();">(Note 8)</span>. The organic phases
are combined and dried over 70 g of Na<sub>2</sub>SO<sub>4</sub>, filtered by vacuum suction through a medium porosity fritted glass funnel, and the solvent is removed under reduced pressure by rotary evaporation (25-45 mmHg,
room temperature water bath) providing the crude product as a yellow oil. The crude product is purified by chromatography on silica gel <span class="hotspot" onclick="javascript:jsToolTipGoto('note18')"
onmouseover="tooltip.show(getItemText('note18'));" onmouseout="tooltip.hide();">(Note 18)</span> to afford 6.64 g (71%) <span class="hotspot" onclick="javascript:jsToolTipGoto('note19')"
onmouseover="tooltip.show(getItemText('note19'));" onmouseout="tooltip.hide();">(Note 19)</span> of the product as a colorless oil <span class="hotspot" onclick="javascript:jsToolTipGoto('note20')"
onmouseover="tooltip.show(getItemText('note20'));" onmouseout="tooltip.hide();">(Note 20)</span>.</div>
</div>
<div class="sectheading">2. Notes</div>
<div class="notesbodies">
<div class="notepara"><a name="note1" id="note1"></a>1. <span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(5445));" onmouseout="tooltip.hide();"
onclick="jsShowCpdTip(5445);">2-Methyl-1,3-cyclohexanedione</span></span> (97%)</span> and <span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(6805));"
onmouseout="tooltip.hide();" onclick="jsShowCpdTip(6805);">trifluoromethane-sulfonic anhydride</span></span> (99%)</span> were purchased from Sigma-Aldrich and used without further purification.</div>
<div class="notepara"><a name="note2" id="note2"></a>2. <span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(270));" onmouseout="tooltip.hide();"
onclick="jsShowCpdTip(270);">Pyridine</span></span> (99%)</span> was purchased from Sigma-Aldrich and stored over KOH pellets.</div>
<div class="notepara"><a name="note3" id="note3"></a>3. Methylene chloride (HPLC Grade) was purchased from Fischer Scientific and purified using an Innovative Technology solvent purification system.</div>
<div class="notepara"><a name="note4" id="note4"></a>4. The indicated temperatures at which reaction mixtures are kept refer to the temperature of external cooling baths as follows: (a) -78 °C cooling bath prepared with dry ice
and acetone, (b) 0 °C cooling bath prepared with ice and water, and (c) -30 °C cooling bath prepared by adding dry ice to acetone and carefully monitoring the bath temperature. No external bath was employed for reactions
conducted at room temperature.</div>
<div class="notepara"><a name="note5" id="note5"></a>5. The highest internal temperature observed by the checkers was -61 °C.</div>
<div class="notepara"><a name="note6" id="note6"></a>6. The submitters observed that a small amount of white precipitate forms during the addition of trifluoromethanesulfonic anhydride.</div>
<div class="notepara"><a name="note7" id="note7"></a>7. Hydrochloric acid (1 M) was prepared by dilution of hydrochloric acid (12.1 M, ACS grade) purchased from EMD Chemicals.</div>
<div class="notepara"><a name="note8" id="note8"></a>8. Ethyl ether (anhydrous, ACS grade) was purchased from EMD Chemicals and used without further purification.</div>
<div class="notepara"><a name="note9" id="note9"></a>9. The submitters obtained a yellow oil.</div>
<div class="notepara"><a name="note10" id="note10"></a>10. The crude product was purified using 300 g of Silica Gel 60 (Geduran(r) 40-63 µM) wet-loaded as a slurry. The sample was loaded in a minimum volume of eluent, passed
through the column using gradient <span class="chemical"><span class="chemname">elution</span> (500 mL of 9:1 hexanes:EtOAc, 500 mL of 8:2 hexanes:EtOAc, and 1000 mL of 7:3 hexanes:EtOAc)</span>, and collected in 20-mL
fractions. Fractions 58-99 were collected, combined, and concentrated under reduced pressure to obtain the final product. The R<sub>f</sub> of 2-methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one = 0.62 and
2-methyl-1,3-cyclohexanedione = 0.22 in 8:2 hexanes:ethyl acetate.</div>
<div class="notepara"><a name="note11" id="note11"></a>11. The compound exhibited the following physical and spectroscopic data: IR (neat): 2964, 1688, 1416, 1344, 1210, 1135, 1024, 912, 891, 793, 759 cm<sup>-1</sup>.
<sup>1</sup>H NMR <a class="pdflink" target="_blank" href="/content/pdfs/Spectrum/v88p0353_H_note11.pdf">pdf</a>(500 MHz, CDCl<sub>3</sub>) δ: 1.77 (d, <i>J</i> = 1.9 Hz, 3 H), 2.05 - 1.97 (apparent pentet, 2 H), 2.40 (t,
<i>J</i> = 7.9 Hz, 2 H), 2.66 (dtd, <i>J</i> = 6.1, 4.0, 1.9 Hz, 2 H); <sup>13</sup>C NMR <a class="pdflink" target="_blank" href="/content/pdfs/Spectrum/v88p0353_C_note11.pdf">pdf</a>(126 MHz, CDCl<sub>3</sub>) δ: 9.0, 20.5,
28.6, 36.5, 118.2 (q, <i>J</i><sub>CF</sub> = 319.8 Hz), 127.9, 162.0, 197.5; HRMS (ESI) calcd. for C<sub>8</sub>H<sub>9</sub>HF<sub>3</sub>O<sub>4</sub>S[M+H]: 259.0246. Found: 259.0246. Anal. calcd. for
C<sub>8</sub>H<sub>9</sub>F<sub>3</sub>O<sub>4</sub>S: C, 37.21; H, 3.51; F, 22.07; S, 12.42. Found: C, 37.32; H, 3.45; F, 21.84; S, 12.41.</div>
<div class="notepara"><a name="note12" id="note12"></a>12. <span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(15875));" onmouseout="tooltip.hide();"
onclick="jsShowCpdTip(15875);">2-Methyl-1,3-dithiane</span></span> (=98%)</span> was purchased from Fluka and used without further purification.</div>
<div class="notepara"><a name="note13" id="note13"></a>13. Tetrahydrofuran (HPLC Grade) was purchased from EMD Chemicals and purified using an Innovative Technology solvent purification system.</div>
<div class="notepara"><a name="note14" id="note14"></a>14. <i>n</i>-Butyllithium (2.5 M solution in hexanes) was purchased from Sigma-Aldrich and titrated using (-)-menthol and 1,10-phenanthroline (= 99%).</div>
<div class="notepara"><a name="note15" id="note15"></a>15. The internal temperature reached -57 °C during addition.</div>
<div class="notepara"><a name="note16" id="note16"></a>16. TLC analysis showed formation of product by TLC (R<i><sub>f</sub></i> (reaction product) = 0.3; R<i><sub>f</sub></i> (2-methyl-1,3-dithiane) = 0.40, R<i><sub>f</sub></i>
(2-methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one) = 0.2; elution with 9:1 hexanes:EtOAc; UV and KMnO<sub>4</sub>/heating visualization). Completion of the reaction is difficult to discern because <i>n</i>-butyllithium
is the limiting reagent, and therefore both the dithiane and triflate remain even after all of the butyllithium has been consumed.</div>
<div class="notepara"><a name="note17" id="note17"></a>17. Half-saturated aqueous ammonium chloride solution was prepared by dilution of a saturated aqueous ammonium chloride solution; <span class="chemical"><span
class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(20));" onmouseout="tooltip.hide();" onclick="jsShowCpdTip(20);">ammonium chloride</span></span> (99.5% ACS)</span> reagent purchased from
Sigma-Aldrich.</div>
<div class="notepara"><a name="note18" id="note18"></a>18. The crude product was purified using 300 g of Silica Gel 60 (Geduran(r) 40-63 µM) wet-loaded as a slurry. The sample was loaded in a minimum volume of eluent, passed
through the column using isocratic elution (2000 mL of 98:2 hexanes:EtOAc), and collected in 20-mL fractions. Fractions 38-85 were collected, combined, and concentrated under reduced pressure to obtain the final product. The
checkers found that excess dithiane complicated isolation of the product. However, most of the excess dithiane could be easily removed by placing the unpurified reaction product under high vacuum overnight. The checkers were
then able to isolate the product using 360 g of silica and 3.5 L of 95:5 hexanes:EtOAc. Fractions of 25 mL were collected, and the product was found in fractions 55-93.</div>
<div class="notepara"><a name="note19" id="note19"></a>19. The checkers observed that yields were improved substantially using freshly distilled dithiane (55 °C, 1 mmHg), recently chromatographed triflate that was concentrated
from anhydrous THF, and a newly opened bottle of butyllithium in hexanes.</div>
<div class="notepara"><a name="note20" id="note20"></a>20. The compound exhibited the following physical and spectroscopic data: IR (neat): 2918, 1700, 1446, 1423, 1372, 1359, 1277, 1243, 1217, 1149, 1071, 998, 907, 868, 673
cm<sup>-1</sup>. <sup>1</sup>H NMR <a class="pdflink" target="_blank" href="/content/pdfs/Spectrum/v88p0353_H_note20.pdf">pdf</a>(400 MHz, CDCl<sub>3</sub>) δ: 1.68 (s, 3 H), 1.87 - 1.71 (m, 6 H), 2.14 - 2.04 (m, 1 H), 2.18 (td,
<i>J</i> = 6.8, 2.6 Hz, 2 H), 2.62 (dt, <i>J</i> = 7.5, 3.5 Hz, 2 H), 2.79 (t, <i>J</i> = 7.2 Hz, 2 H), 3.10 (t, <i>J</i> = 13.7 Hz, 2 H); <sup>13</sup>C NMR
<a class="pdflink" target="_blank" href="/content/pdfs/Spectrum/v88p0353_C_note20.pdf">pdf</a>(126 MHz, CDCl<sub>3</sub>) δ: 3.6, 18.2, 24.1, 24.3, 25.0, 28.2, 34.6, 54.8, 76.5, 78.3, 203.9. HRMS (ESI) calcd. for
C<sub>12</sub>H<sub>18</sub>HOS<sub>2</sub>[M+H]: 243.0872. Found: 243.0873. Anal. calcd. for C<sub>12</sub>H<sub>18</sub>OS<sub>2</sub>: C, 59.46; H, 7.48; S, 26.46. Found: C, 59.48; H, 7.25; S, 26.59.
<b>Safety and Waste Disposal Information</b> All hazardous materials should be handled and disposed of in accordance with "Prudent Practices in the Laboratory"; National Academy Press; Washington, DC, 1995. </div>
</div>
<div class="sectheading">Working with Hazardous Chemicals</div>
<div class="wasteinfopara">
<p style="line-height:130%!important;">The procedures in <i>Organic Syntheses </i>are intended for use only by persons with proper training in experimental organic chemistry. All hazardous materials should be handled using the
standard procedures for work with chemicals described in references such as "Prudent Practices in the Laboratory" (The National Academies Press, Washington, D.C., 2011; the full text can be accessed free of charge at
<a href="http://www.nap.edu/catalog.php?record_id=12654">http://www.nap.edu/catalog.php?record_id=12654</a>). All chemical waste should be disposed of in accordance with local regulations. For general guidelines for the
management of chemical waste, see Chapter 8 of Prudent Practices. </p>
<p style="line-height:130%!important;"> In some articles in <i>Organic Syntheses</i>, chemical-specific hazards are highlighted in red "Caution Notes" within a procedure. It is important to recognize that the absence of a caution
note does not imply that no significant hazards are associated with the chemicals involved in that procedure. Prior to performing a reaction, a thorough risk assessment should be carried out that includes a review of the
potential hazards associated with each chemical and experimental operation on the scale that is planned for the procedure. Guidelines for carrying out a risk assessment and for analyzing the hazards associated with chemicals can
be found in Chapter 4 of Prudent Practices.</p>
<p style="line-height:130%!important;"> The procedures described in <i>Organic Syntheses</i> are provided as published and are conducted at one's own risk. Organic Syntheses, Inc., its Editors, and its Board of Directors do not
warrant or guarantee the safety of individuals using these procedures and hereby disclaim any liability for any injuries or damages claimed to have resulted from or related in any way to the procedures herein.</p>
<p style="line-height:130%!important;"><i>The paragraphs above were added in September, 2014. The statements above do not supersede any specific hazard caution notes and safety instructions included in the procedure.</i></p>
</div>
<div class="sectheading">3. Discussion</div>
<div class="discussionpara">Alkyne building blocks offer many advantages in chemical synthesis owing to their high enthalpic (chemical potential energy) content and orthogonal reactivity with respect to other common organic
functional groups.<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref2'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref2">2</a></span></sup> The advent of late transition
metal catalysts that display a preference for coordination to π-systems has expanded the scope of alkyne reactions and further increased their
value.<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref3'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref3">3</a></span></sup></div>
<div class="discussionpara">As the scope of alkyne reactions continues to expand, so too does the demand for efficient synthetic methods that produce key alkyne building blocks. However, the energy-rich alkyne π-system is not easy
to generate. Functionalized alkynes are typically prepared using methods that make use of simpler alkyne starting materials, like acetylide coupling. Common methods for the generation of alkyne π-bonds from non-acetylenic starting
materials include elimination, vinylidene carbene rearrangement, and fragmentation
reactions.<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref4'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref4">4</a></span></sup></div>
<div class="discussionpara">Vinylogous acyl triflates (VATs) undergo tandem nucleophilic addition / fragmentation reactions to provide tethered
keto-alkynes.<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref5'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref5">5</a></span></sup> The overall sequence achieves the
conversion of symmetric, cyclic diones into acyclic alkynyl ketones that comprise orthogonal and non-contiguous functionalities. The stability of the triflate anion (an excellent leaving group) enables the fragmentation process in
much the same way as formation of molecular nitrogen is a driving force in the classic Eschenmoser-Tanabe
reaction.<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref6'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref6">6</a></span></sup> These mechanistically related reactions are
among the few C-C bond cleaving fragmentations that produce alkyne
π-systems.<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref7'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref7">7</a></span></sup></div>
<div class="discussionpara">
<div class="figcaption"><b>Scheme 1.</b> Alternative strategies for the synthesis of (<i>Z</i>)-6-heneicosen-11-one</div>
<div style="text-align:center;margin:1em"><img src="/content/figures/v88p0353-2.gif" align="middle" alt="Scheme 1. Alternative strategies for the synthesis of (Z)-6-heneicosen-11-one"></div>
</div>
<div class="discussionpara">The utility of carbanion-triggered fragmentation of vinylogous acyl triflates as a modern alternative to the Eschenmoser-Tanabe fragmentation is illustrated in the synthesis of
(<i>Z</i>)-6-heneicosen-11-one, the sex pheromone of the Douglas fir tussock moth (Figure 1). In an earlier
approach,<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref8'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref8">8</a></span></sup> a cyclic vinylogous methyl ester was
treated with <i>n</i>-decyl Grignard in an addition-hydrolysis sequence to set up the multi-stage Eschenmoser-Tanabe process. Using the current method, nucleophilic addition of the same Grignard reagent to the corresponding
vinylogous triflate triggered fragmentation directly.<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref9'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref9">9</a></span></sup>
The streamlined entry into the fragmentation pathway provides an increased overall yield in fewer steps, and it avoids acidic conditions and the sometimes-troublesome preparation of cyclic enone
oxides.<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref6'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref6">6b</a></span></sup></div>
<div class="discussionpara">The scope of appropriate nucleophiles is illustrated in Table 1. Carbanion reagents were the first nucleophiles to be
explored,<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref5'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref5">5</a></span></sup> as these provide alkyl and aryl ketones of
the type most closely associated with the Eschenmoser-Tanabe fragmentation (entries 1-4, 10-12). The typical reaction is conducted by treating the nucleophile with the vinylogous acyl triflate in THF at low temperature to achieve
the initial 1,2-addition, and then warming the reaction mixture to room temperature or above to promote the (entropically favorable) fragmentation event. It has been observed experimentally that addition / fragmentation reactions
using unstabilized </div>
<div class="discussionpara">
<div class="figcaption"><b>Table 1.</b> Scope of the addition/fragmentation reaction</div>
<div style="text-align:center;margin:1em"><img src="/content/figures/v88p0353-3.gif" align="middle" alt="Table 1. Scope of the addition/fragmentation reaction"></div>
</div>
<div class="discussionpara">alkyllithium and alkyl Grignard reagents occur more efficiently in toluene than in THF (entry
2);<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref9'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref9">9</a></span></sup> this observation may be attributable to
solvent-dependent aggregation states of the organometallic reagent. In toluene, higher aggregation states of the nucleophile likely attenuate its reactivity and promote selectivity for the desired 1,2-addition over alternative
pathways like proton- or electron-transfer.</div>
<div class="discussionpara">Addition of stabilized carbanion nucleophiles to vinylogous acyl triflates triggers what we term the
VAT-Claisen<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref10'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref10">10</a></span></sup> reaction: a ring-opening fragmentation
to give acyclic β-keto ester and related products much like those observed traditionally in the Claisen condensation (entries 5-6). Whereas the Claisen condensation is driven by deprotonation of final product, the VAT-Claisen
reaction is rendered irreversible by the fragmentation event. Deprotonation of the final VAT-Claisen product may still occur incidentally, in which case the use of excess nucleophile is required to realize complete conversion
(entry 5).</div>
<div class="discussionpara">Other suitable nucleophiles for promoting fragmentation include primary lithium amides (entry 7) and lithium triethylborohydride (entry
8).<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref5'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref5">5</a></span></sup> Diisobutylaluminum hydride reduces the VAT
carbonyl but does not trigger fragmentation; the resulting alcohol can then be treated with excess Grignard reagents to promote fragmentation and in situ trapping of the resultant aldehyde (entry
9).<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref11'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref11">11</a></span></sup> Other suitable VAT substrates are shown in
entries 10-12. The five- and seven-membered ring VATs are less stable than their hexacyclic counterparts, and as such they are best prepared immediately prior to use.</div>
<div class="discussionpara">The tandem nucleophilic addition / fragmentation of cyclic VAT substrates provides an alternative entry into the classic Eschenmoser-Tanabe pathway, one of the few Grob-type fragmentations capable of
generating alkyne π-bonds. The method outlined above delivers orthogonally functionalized acyclic building blocks - alkynyl ketones and related compounds - from symmetrical cyclic dione starting materials. This methodology
continues to evolve; application to the synthesis of natural
products,<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref12'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref12">12</a></span></sup> homopropargyl
alcohol<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref13'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref13">13</a></span></sup> and homopropargyl
amine<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref14'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref14">14</a></span></sup> derivatives from heterocyclic VATs, and
other challenging classes of organic compounds<sup><span class="hotspot" onmouseover="tooltip.show(getItemText('ref15'));" onmouseout="tooltip.hide();"><a target="_self" href="demo.aspx?prep=v88p0353#ref15">15</a></span></sup> are
underway at this time.</div>
<hr>
<div class="footnotes">
<div class="footnotehead">References and Notes</div>
<ol class="footnotelist">
<li class="footnoteitem"><span class="footnotecontent"><a name="ref1" id="ref1"></a>Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390, USA. E-Mail: gdudley@chem.fsu.edu This work was
supported by a grant from the National Science Foundation (NSF-CHE 0749918). M.P.L. is a recipient of the Capes-Fulbright Graduate Research Fellowship (2008). T.T.H. is a recipient of the Vietnam Education Foundation (VEF)
Graduate Fellowship (2009).</span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref2" id="ref2"></a>All-Carbon Functions Polyynes, Arynes, Enynes, and Alkynes. In <i>Science of Synthesis: Houben-Weyl Methods of Molecular Transformation;</i>
Thomas, E. J., Hopf, H., Eds., Thieme: Stuttgart, 2008; Vol. 43.</span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref3" id="ref3"></a>(a) Tsuji, J. <i>Transition Metal Reagents and Catalysts: Innovations in Organic Synthesis</i>; Wiley & Sons: New York, 2000. (b)
<i>Lewis Acids in Organic Synthesis; Yamamoto</i>, H., Ed.; Wiley-VCH: New York, 2000.</span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref4" id="ref4"></a>(a) Larock, R. C. <i>Comprehensive Organic Transformations,</i> 2nd Ed.; Wiley & Sons: New York, 1999; pp 563-583. (b) Brandsma, L.
Preparative Acetylenic Chemistry, 2nd Ed.; Elsevier: Amsterdam, 1988.</span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref5" id="ref5"></a>(a) Kamijo, S.; Dudley, G. B. <i>J. Am. Chem. Soc.</i> <b>2005</b>, <i>127</i>,
5028-5029.<a target="_blank" href="https://doi.org/10.1021/JA050663M">[CrossRef]</a> (b) Kamijo, S.; Dudley, G. B. <i>J. Am. Chem. Soc.</i> <b>2006</b>, <i>128</i>, 6499-6507; Addition/Correction: <i>J. Am. Chem. Soc.</i>
<b>2010</b>, <i>132</i>, 8223.<a target="_blank" href="https://doi.org/10.1021/JA0608085">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref6" id="ref6"></a>(a) Eschenmoser, A.; Felix, D.; Ohloff, G. <i>Helv. Chim. Acta</i> <b>1967</b>, <i>50</i>,
708-713.<a target="_blank" href="https://doi.org/10.1002/HLCA.19670500232">[CrossRef]</a> (b) Tanabe, M.; Crowe, D. F.; Dehn, R. L. <i>Tetrahedron Lett.</i> <b>1967</b>,
3943-3946.<a target="_blank" href="https://doi.org/10.1016/S0040-4039(01)89757-4">[CrossRef]</a> (c) Grob, C. A.; Schiess, P. W. H. <i>Angew. Chem., Int. Ed. Engl.</i> <b>1967</b>, <i>6</i>,
1-15.<a target="_blank" href="https://doi.org/10.1002/ANIE.196700011">[CrossRef]</a> (d) Weyerstahl, P.; Marschall, H. In <i>Comprehensive Organic Synthesis</i>, Trost, B. M., Fleming, I., Eds.; Pergamon Press: Elmsford, NY,
1991; Vol. 6, pp 1041-1070.<a target="_blank" href="https://doi.org/10.1016/B978-0-08-052349-1.00179-7">[CrossRef]</a> (e) Prantz, K.; Mulzer, J. <i>Chem. Rev</i>. <b>2010</b>, <i>110</i>,
3741-3766.<a target="_blank" href="https://doi.org/10.1021/CR900386H">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref7" id="ref7"></a>(a) For an early example driven by formation of carbon dioxide, see: Grob, C. A.; Csapilla, J. Cseh, G. <i>Helv. Chim. Acta</i> <b>1964</b>,
<i>47</i>, 1590-1602.<a target="_blank" href="https://doi.org/10.1002/HLCA.19640470621">[CrossRef]</a> (b) For recent examples driven by formation of molecular nitrogen, see: Draghici, C.; Brewer, M. <i>J. Am. Chem. Soc.</i>
<b>2008</b>, <i>130</i>, 3766-3767;<a target="_blank" href="https://doi.org/10.1021/JA801004D">[CrossRef]</a> (c) Draghici, C.; Huang, Q.; Brewer, M. <i>J. Org. Chem.</i> <b>2009</b>, <i>74</i>,
8410-8413;<a target="_blank" href="https://doi.org/10.1021/JO901978Y">[CrossRef]</a> (d) Bayir, A.; Draghici, C.; Brewer, M. <i>J. Org. Chem.</i> <b>2010</b>, <i>75</i>,
296-302.<a target="_blank" href="https://doi.org/10.1021/JO902405F">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref8" id="ref8"></a>Kocienski, P. J.; Cernigliaro, G. J. <i>J. Org. Chem.</i> <b>1976</b>, <i>41</i>,
2927-2928.<a target="_blank" href="https://doi.org/10.1021/JO00879A029">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref9" id="ref9"></a>Jones, D. M.; Kamijo, S.; Dudley, G. B. <i>Synlett</i> <b>2006</b>, 936-938. </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref10" id="ref10"></a>(a) Kamijo, S.; Dudley, G. B. <i>Org. Lett.</i> <b>2006</b>, <i>8,</i>
175-177.<a target="_blank" href="https://doi.org/10.1021/OL0527781">[CrossRef]</a> (b) Jones, D. M.; Lisboa, M. P.; Kamijo, S.; Dudley, G. B. <i>J. Org. Chem.</i> <b>2010</b>, <i>75</i>,
3260-3267.<a target="_blank" href="https://doi.org/10.1021/JO100249G">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref11" id="ref11"></a>Kamijo, S.; Dudley, G. B. <i>Tetrahedron Lett.</i> <b>2006</b>, <i>47</i>,
5629-5632.<a target="_blank" href="https://doi.org/10.1016/J.TETLET.2006.06.040">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref12" id="ref12"></a>Jones, D. M.; Dudley, G. B. <i>Synlett</i> <b>2010</b>, 223-226. </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref13" id="ref13"></a>Tummatorn, J.; Dudley, G. B. <i>J. Am. Chem. Soc.</i> <b>2008</b>, <i>130</i>,
5050-5051.<a target="_blank" href="https://doi.org/10.1021/JA801018R">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref14" id="ref14"></a>Tummatorn, J.; Dudley, G. B. <i>Org. Lett.</i> <b>2011</b>, <i>13</i>,
158-160.<a target="_blank" href="https://doi.org/10.1021/OL102760Q">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref15" id="ref15"></a>Jones, D. M.; Dudley, G. B. <i>Tetrahedron</i> <b>2010</b>, <i>66</i>,
4860-4866.<a target="_blank" href="https://doi.org/10.1016/J.TET.2010.03.014">[CrossRef]</a> </span></li>
</ol>
</div>
<hr>
<div class="cpdlist">
<p class="cpdcaption">Appendix<br> Chemical Abstracts Nomenclature (Collective Index Number);<br> (Registry Number)</p>
<p class="cpdchemical" id="chem_15876"><span class="chemname">2-Methyl-2-(1-oxo-5-heptynyl)-1,3-dithiane: 5-Heptyn-1-one, 1-(2-methyl-1,3-dithian-2-yl)-</span>; (892874-94-1)</p>
<p class="cpdchemical" id="chem_15875"><span class="chemname">2-Methyl-1,3-dithiane</span>; (6007-26-7)</p>
<p class="cpdchemical" id="chem_1885"><span class="chemname"><i>n</i>-Butyllithium</span>; (109-72-8)</p>
<p class="cpdchemical" id="chem_15877"><span class="chemname">2-Methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one: Methanesulfonic acid, 1,1,1-trifluoro-, 2-methyl-3-oxo-1-cyclohexen-1-yl ester</span>; (150765-78-9)</p>
<p class="cpdchemical" id="chem_5445"><span class="chemname">2-Methyl-1,3-cyclohexanedione</span>; (1193-55-1)</p>
<p class="cpdchemical" id="chem_6805"><span class="chemname">Trifluoromethanesulfonic anhydride</span>; (358-23-6)</p>
</div>
<div class="authlist">
<table border="0" cellpadding="10px" cellspacing="10px">
<tbody>
<tr>
<td><img src="/content/authors/v88p0353gregoryb.jpg" width="100%"></td>
<td> Gregory B. Dudley received a B.A. from FSU in 1995 and a Ph.D. in 2000 under the direction of Professor Rick Danheiser at MIT. After completing an NIH Postdoctoral Fellowship with Professor Samuel Danishefsky at the
Sloan-Kettering Institute for Cancer Research, he returned to FSU as an assistant professor in 2002. Professor Dudley was promoted to associate professor with tenure in 2008. The current mission of his research program is
to impact the drug discovery process by contributing fundamental new knowledge in organic synthesis. The addition / fragmentation methodology featured herein has figured prominently in this effort over the past few years.
</td>
</tr>
<tr>
<td><img src="/content/authors/v88p0353marildap.jpg" width="100%"></td>
<td> Marilda P. Lisboa was born in Rio de Janeiro and raised in Minas Gerais, Brazil. She received her B.S. degree in pharmacy in 2005 and M.S. degree in pharmaceutical sciences in 2007 from the Federal University of Minas
Gerais, Brazil. In 2008, she was awarded a Capes-Fulbright fellowship to pursue her PhD in Chemistry at Florida State University. Currently, she is a PhD student under the supervision of Professor Gregory Dudley and her
research is focused on the synthesis of the natural product palmerolide A. </td>
</tr>
<tr>
<td><img src="/content/authors/v88p0353tungt.jpg" width="100%"></td>
<td> Tung T. Hoang was born in Ha Long, a small yet beautiful city known for the Ha Long Bay with thousands of islets and its sunshine beach in northeast Vietnam. Inspired by his high school teacher, Tung entered the
chemistry program of Vietnam National University where he earned his B.A. degree in 2006. As a recipient of the Vietnam Education Foundation Fellowship cohort 2009, he went to Florida State University to pursue his PhD in
organic chemistry. Tung is currently working under the direction of Professor Gregory Dudley with interest in the total syntheses of biologically active natural products. </td>
</tr>
<tr>
<td><img src="/content/authors/v88p0353jimmiew.jpg" width="100%"></td>
<td> Jimmie Weaver was born in 1981 in Oklahoma (US). He studied at Southern Nazarene University where he obtained his B.S. degree in chemistry in 2004. After spending the next year working under William Hildebrand (OUHSC)
in an immunology lab, he began his graduate studies at the University of Kansas under the supervision of Jon Tunge. The primary focus of his graduate work was the synthesis and decarboxylative coupling of a-sulfonyl acetic
esters. He completed his Ph.D. in the spring of 2010 and began a post-doctoral fellowship under the direction of Jon Ellman (Yale) where he is currently working on organocatalysis and drug delivery projects. </td>
</tr>
</tbody>
</table>
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<h2 class="acc_trigger active">
<a href="#">Notes</a>
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<p><a name="note1" id="note1"></a>1. <span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(5445));" onmouseout="tooltip.hide();"
onclick="jsShowCpdTip(5445);">2-Methyl-1,3-cyclohexanedione</span></span> (97%)</span> and <span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(6805));"
onmouseout="tooltip.hide();" onclick="jsShowCpdTip(6805);">trifluoromethane-sulfonic anhydride</span></span> (99%)</span> were purchased from Sigma-Aldrich and used without further purification.</p>
<p><a name="note2" id="note2"></a>2. <span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(270));" onmouseout="tooltip.hide();"
onclick="jsShowCpdTip(270);">Pyridine</span></span> (99%)</span> was purchased from Sigma-Aldrich and stored over KOH pellets.</p>
<p><a name="note3" id="note3"></a>3. Methylene chloride (HPLC Grade) was purchased from Fischer Scientific and purified using an Innovative Technology solvent purification system.</p>
<p><a name="note4" id="note4"></a>4. The indicated temperatures at which reaction mixtures are kept refer to the temperature of external cooling baths as follows: (a) -78 °C cooling bath prepared with dry ice and acetone,
(b) 0 °C cooling bath prepared with ice and water, and (c) -30 °C cooling bath prepared by adding dry ice to acetone and carefully monitoring the bath temperature. No external bath was employed for reactions conducted at
room temperature.</p>
<p><a name="note5" id="note5"></a>5. The highest internal temperature observed by the checkers was -61 °C.</p>
<p><a name="note6" id="note6"></a>6. The submitters observed that a small amount of white precipitate forms during the addition of trifluoromethanesulfonic anhydride.</p>
<p><a name="note7" id="note7"></a>7. Hydrochloric acid (1 M) was prepared by dilution of hydrochloric acid (12.1 M, ACS grade) purchased from EMD Chemicals.</p>
<p><a name="note8" id="note8"></a>8. Ethyl ether (anhydrous, ACS grade) was purchased from EMD Chemicals and used without further purification.</p>
<p><a name="note9" id="note9"></a>9. The submitters obtained a yellow oil.</p>
<p><a name="note10" id="note10"></a>10. The crude product was purified using 300 g of Silica Gel 60 (Geduran(r) 40-63 µM) wet-loaded as a slurry. The sample was loaded in a minimum volume of eluent, passed through the
column using gradient <span class="chemical"><span class="chemname">elution</span> (500 mL of 9:1 hexanes:EtOAc, 500 mL of 8:2 hexanes:EtOAc, and 1000 mL of 7:3 hexanes:EtOAc)</span>, and collected in 20-mL fractions.
Fractions 58-99 were collected, combined, and concentrated under reduced pressure to obtain the final product. The R<sub>f</sub> of 2-methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one = 0.62 and
2-methyl-1,3-cyclohexanedione = 0.22 in 8:2 hexanes:ethyl acetate.</p>
<p><a name="note11" id="note11"></a>11. The compound exhibited the following physical and spectroscopic data: IR (neat): 2964, 1688, 1416, 1344, 1210, 1135, 1024, 912, 891, 793, 759 cm<sup>-1</sup>. <sup>1</sup>H NMR
<a class="pdflink" target="_blank" href="/content/pdfs/Spectrum/v88p0353_H_note11.pdf">pdf</a>(500 MHz, CDCl<sub>3</sub>) δ: 1.77 (d, <i>J</i> = 1.9 Hz, 3 H), 2.05 - 1.97 (apparent pentet, 2 H), 2.40 (t, <i>J</i> = 7.9
Hz, 2 H), 2.66 (dtd, <i>J</i> = 6.1, 4.0, 1.9 Hz, 2 H); <sup>13</sup>C NMR <a class="pdflink" target="_blank" href="/content/pdfs/Spectrum/v88p0353_C_note11.pdf">pdf</a>(126 MHz, CDCl<sub>3</sub>) δ: 9.0, 20.5, 28.6,
36.5, 118.2 (q, <i>J</i><sub>CF</sub> = 319.8 Hz), 127.9, 162.0, 197.5; HRMS (ESI) calcd. for C<sub>8</sub>H<sub>9</sub>HF<sub>3</sub>O<sub>4</sub>S[M+H]: 259.0246. Found: 259.0246. Anal. calcd. for
C<sub>8</sub>H<sub>9</sub>F<sub>3</sub>O<sub>4</sub>S: C, 37.21; H, 3.51; F, 22.07; S, 12.42. Found: C, 37.32; H, 3.45; F, 21.84; S, 12.41.</p>
<p><a name="note12" id="note12"></a>12. <span class="chemical"><span class="chemname"><span class="hotspot" onmouseover="tooltip.show(jsLoadCpd(15875));" onmouseout="tooltip.hide();"
onclick="jsShowCpdTip(15875);">2-Methyl-1,3-dithiane</span></span> (=98%)</span> was purchased from Fluka and used without further purification.</p>
<p><a name="note13" id="note13"></a>13. Tetrahydrofuran (HPLC Grade) was purchased from EMD Chemicals and purified using an Innovative Technology solvent purification system.</p>
<p><a name="note14" id="note14"></a>14. <i>n</i>-Butyllithium (2.5 M solution in hexanes) was purchased from Sigma-Aldrich and titrated using (-)-menthol and 1,10-phenanthroline (= 99%).</p>
<p><a name="note15" id="note15"></a>15. The internal temperature reached -57 °C during addition.</p>
<p><a name="note16" id="note16"></a>16. TLC analysis showed formation of product by TLC (R<i><sub>f</sub></i> (reaction product) = 0.3; R<i><sub>f</sub></i> (2-methyl-1,3-dithiane) = 0.40, R<i><sub>f</sub></i>
(2-methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one) = 0.2; elution with 9:1 hexanes:EtOAc; UV and KMnO<sub>4</sub>/heating visualization). Completion of the reaction is difficult to discern because
<i>n</i>-butyllithium is the limiting reagent, and therefore both the dithiane and triflate remain even after all of the butyllithium has been consumed.</p>
<p><a name="note17" id="note17"></a>17. Half-saturated aqueous ammonium chloride solution was prepared by dilution of a saturated aqueous ammonium chloride solution; <span class="chemical"><span class="chemname"><span
class="hotspot" onmouseover="tooltip.show(jsLoadCpd(20));" onmouseout="tooltip.hide();" onclick="jsShowCpdTip(20);">ammonium chloride</span></span> (99.5% ACS)</span> reagent purchased from Sigma-Aldrich.</p>
<p><a name="note18" id="note18"></a>18. The crude product was purified using 300 g of Silica Gel 60 (Geduran(r) 40-63 µM) wet-loaded as a slurry. The sample was loaded in a minimum volume of eluent, passed through the
column using isocratic elution (2000 mL of 98:2 hexanes:EtOAc), and collected in 20-mL fractions. Fractions 38-85 were collected, combined, and concentrated under reduced pressure to obtain the final product. The
checkers found that excess dithiane complicated isolation of the product. However, most of the excess dithiane could be easily removed by placing the unpurified reaction product under high vacuum overnight. The checkers
were then able to isolate the product using 360 g of silica and 3.5 L of 95:5 hexanes:EtOAc. Fractions of 25 mL were collected, and the product was found in fractions 55-93.</p>
<p><a name="note19" id="note19"></a>19. The checkers observed that yields were improved substantially using freshly distilled dithiane (55 °C, 1 mmHg), recently chromatographed triflate that was concentrated from anhydrous
THF, and a newly opened bottle of butyllithium in hexanes.</p>
<p><a name="note20" id="note20"></a>20. The compound exhibited the following physical and spectroscopic data: IR (neat): 2918, 1700, 1446, 1423, 1372, 1359, 1277, 1243, 1217, 1149, 1071, 998, 907, 868, 673 cm<sup>-1</sup>.
<sup>1</sup>H NMR <a class="pdflink" target="_blank" href="/content/pdfs/Spectrum/v88p0353_H_note20.pdf">pdf</a>(400 MHz, CDCl<sub>3</sub>) δ: 1.68 (s, 3 H), 1.87 - 1.71 (m, 6 H), 2.14 - 2.04 (m, 1 H), 2.18 (td, <i>J</i>
= 6.8, 2.6 Hz, 2 H), 2.62 (dt, <i>J</i> = 7.5, 3.5 Hz, 2 H), 2.79 (t, <i>J</i> = 7.2 Hz, 2 H), 3.10 (t, <i>J</i> = 13.7 Hz, 2 H); <sup>13</sup>C NMR
<a class="pdflink" target="_blank" href="/content/pdfs/Spectrum/v88p0353_C_note20.pdf">pdf</a>(126 MHz, CDCl<sub>3</sub>) δ: 3.6, 18.2, 24.1, 24.3, 25.0, 28.2, 34.6, 54.8, 76.5, 78.3, 203.9. HRMS (ESI) calcd. for
C<sub>12</sub>H<sub>18</sub>HOS<sub>2</sub>[M+H]: 243.0872. Found: 243.0873. Anal. calcd. for C<sub>12</sub>H<sub>18</sub>OS<sub>2</sub>: C, 59.46; H, 7.48; S, 26.46. Found: C, 59.48; H, 7.25; S, 26.59.
<b>Safety and Waste Disposal Information</b> All hazardous materials should be handled and disposed of in accordance with "Prudent Practices in the Laboratory"; National Academy Press; Washington, DC, 1995. </p>
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<h2 class="acc_trigger">
<a href="#">References/EndNotes</a>
</h2>
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<ol>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref1" id="ref1"></a>Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390, USA. E-Mail: gdudley@chem.fsu.edu This
work was supported by a grant from the National Science Foundation (NSF-CHE 0749918). M.P.L. is a recipient of the Capes-Fulbright Graduate Research Fellowship (2008). T.T.H. is a recipient of the Vietnam Education
Foundation (VEF) Graduate Fellowship (2009).</span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref2" id="ref2"></a>All-Carbon Functions Polyynes, Arynes, Enynes, and Alkynes. In
<i>Science of Synthesis: Houben-Weyl Methods of Molecular Transformation;</i> Thomas, E. J., Hopf, H., Eds., Thieme: Stuttgart, 2008; Vol. 43.</span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref3" id="ref3"></a>(a) Tsuji, J. <i>Transition Metal Reagents and Catalysts: Innovations in Organic Synthesis</i>; Wiley & Sons: New York, 2000. (b)
<i>Lewis Acids in Organic Synthesis; Yamamoto</i>, H., Ed.; Wiley-VCH: New York, 2000.</span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref4" id="ref4"></a>(a) Larock, R. C. <i>Comprehensive Organic Transformations,</i> 2nd Ed.; Wiley & Sons: New York, 1999; pp 563-583. (b) Brandsma,
L. Preparative Acetylenic Chemistry, 2nd Ed.; Elsevier: Amsterdam, 1988.</span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref5" id="ref5"></a>(a) Kamijo, S.; Dudley, G. B. <i>J. Am. Chem. Soc.</i> <b>2005</b>, <i>127</i>,
5028-5029.<a target="_blank" href="https://doi.org/10.1021/JA050663M">[CrossRef]</a> (b) Kamijo, S.; Dudley, G. B. <i>J. Am. Chem. Soc.</i> <b>2006</b>, <i>128</i>, 6499-6507; Addition/Correction:
<i>J. Am. Chem. Soc.</i> <b>2010</b>, <i>132</i>, 8223.<a target="_blank" href="https://doi.org/10.1021/JA0608085">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref6" id="ref6"></a>(a) Eschenmoser, A.; Felix, D.; Ohloff, G. <i>Helv. Chim. Acta</i> <b>1967</b>, <i>50</i>,
708-713.<a target="_blank" href="https://doi.org/10.1002/HLCA.19670500232">[CrossRef]</a> (b) Tanabe, M.; Crowe, D. F.; Dehn, R. L. <i>Tetrahedron Lett.</i> <b>1967</b>,
3943-3946.<a target="_blank" href="https://doi.org/10.1016/S0040-4039(01)89757-4">[CrossRef]</a> (c) Grob, C. A.; Schiess, P. W. H. <i>Angew. Chem., Int. Ed. Engl.</i> <b>1967</b>, <i>6</i>,
1-15.<a target="_blank" href="https://doi.org/10.1002/ANIE.196700011">[CrossRef]</a> (d) Weyerstahl, P.; Marschall, H. In <i>Comprehensive Organic Synthesis</i>, Trost, B. M., Fleming, I., Eds.; Pergamon Press:
Elmsford, NY, 1991; Vol. 6, pp 1041-1070.<a target="_blank" href="https://doi.org/10.1016/B978-0-08-052349-1.00179-7">[CrossRef]</a> (e) Prantz, K.; Mulzer, J. <i>Chem. Rev</i>. <b>2010</b>, <i>110</i>,
3741-3766.<a target="_blank" href="https://doi.org/10.1021/CR900386H">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref7" id="ref7"></a>(a) For an early example driven by formation of carbon dioxide, see: Grob, C. A.; Csapilla, J. Cseh, G. <i>Helv. Chim. Acta</i>
<b>1964</b>, <i>47</i>, 1590-1602.<a target="_blank" href="https://doi.org/10.1002/HLCA.19640470621">[CrossRef]</a> (b) For recent examples driven by formation of molecular nitrogen, see: Draghici, C.; Brewer, M.
<i>J. Am. Chem. Soc.</i> <b>2008</b>, <i>130</i>, 3766-3767;<a target="_blank" href="https://doi.org/10.1021/JA801004D">[CrossRef]</a> (c) Draghici, C.; Huang, Q.; Brewer, M. <i>J. Org. Chem.</i> <b>2009</b>,
<i>74</i>, 8410-8413;<a target="_blank" href="https://doi.org/10.1021/JO901978Y">[CrossRef]</a> (d) Bayir, A.; Draghici, C.; Brewer, M. <i>J. Org. Chem.</i> <b>2010</b>, <i>75</i>,
296-302.<a target="_blank" href="https://doi.org/10.1021/JO902405F">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref8" id="ref8"></a>Kocienski, P. J.; Cernigliaro, G. J. <i>J. Org. Chem.</i> <b>1976</b>, <i>41</i>,
2927-2928.<a target="_blank" href="https://doi.org/10.1021/JO00879A029">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref9" id="ref9"></a>Jones, D. M.; Kamijo, S.; Dudley, G. B. <i>Synlett</i> <b>2006</b>, 936-938. </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref10" id="ref10"></a>(a) Kamijo, S.; Dudley, G. B. <i>Org. Lett.</i> <b>2006</b>, <i>8,</i>
175-177.<a target="_blank" href="https://doi.org/10.1021/OL0527781">[CrossRef]</a> (b) Jones, D. M.; Lisboa, M. P.; Kamijo, S.; Dudley, G. B. <i>J. Org. Chem.</i> <b>2010</b>, <i>75</i>,
3260-3267.<a target="_blank" href="https://doi.org/10.1021/JO100249G">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref11" id="ref11"></a>Kamijo, S.; Dudley, G. B. <i>Tetrahedron Lett.</i> <b>2006</b>, <i>47</i>,
5629-5632.<a target="_blank" href="https://doi.org/10.1016/J.TETLET.2006.06.040">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref12" id="ref12"></a>Jones, D. M.; Dudley, G. B. <i>Synlett</i> <b>2010</b>, 223-226. </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref13" id="ref13"></a>Tummatorn, J.; Dudley, G. B. <i>J. Am. Chem. Soc.</i> <b>2008</b>, <i>130</i>,
5050-5051.<a target="_blank" href="https://doi.org/10.1021/JA801018R">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref14" id="ref14"></a>Tummatorn, J.; Dudley, G. B. <i>Org. Lett.</i> <b>2011</b>, <i>13</i>,
158-160.<a target="_blank" href="https://doi.org/10.1021/OL102760Q">[CrossRef]</a> </span></li>
<li class="footnoteitem"><span class="footnotecontent"><a name="ref15" id="ref15"></a>Jones, D. M.; Dudley, G. B. <i>Tetrahedron</i> <b>2010</b>, <i>66</i>,
4860-4866.<a target="_blank" href="https://doi.org/10.1016/J.TET.2010.03.014">[CrossRef]</a> </span></li>
</ol>
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<h2 class="acc_trigger">
<a href="#">Article Compounds</a>
</h2>
<div class="acc_container" style="height: 800px; overflow: auto; display: none;">
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<tbody>
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<td><img style=" width: 50px; " src="/httphandlers/substancetooltip.ashx?id=15876" onmouseover="tooltip.show(jsLoadCpd(15876));" onmouseout="tooltip.hide();" alt="No structure"></td>
<td><span class="chemname">2-Methyl-2-(1-oxo-5-heptynyl)-1,3-dithiane: 5-Heptyn-1-one, 1-(2-methyl-1,3-dithian-2-yl)-</span>; (892874-94-1)</td>
</tr>
<tr>
<td><img style=" width: 50px; " src="/httphandlers/substancetooltip.ashx?id=15875" onmouseover="tooltip.show(jsLoadCpd(15875));" onmouseout="tooltip.hide();" alt="No structure"></td>
<td><span class="chemname">2-Methyl-1,3-dithiane</span>; (6007-26-7)</td>
</tr>
<tr>
<td><img style=" width: 50px; " src="/httphandlers/substancetooltip.ashx?id=1885" onmouseover="tooltip.show(jsLoadCpd(1885));" onmouseout="tooltip.hide();" alt="No structure"></td>
<td><span class="chemname"><i>n</i>-Butyllithium</span>; (109-72-8)</td>
</tr>
<tr>
<td><img style=" width: 50px; " src="/httphandlers/substancetooltip.ashx?id=15877" onmouseover="tooltip.show(jsLoadCpd(15877));" onmouseout="tooltip.hide();" alt="No structure"></td>
<td><span class="chemname">2-Methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one: Methanesulfonic acid, 1,1,1-trifluoro-, 2-methyl-3-oxo-1-cyclohexen-1-yl ester</span>; (150765-78-9)</td>
</tr>
<tr>
<td><img style=" width: 50px; " src="/httphandlers/substancetooltip.ashx?id=5445" onmouseover="tooltip.show(jsLoadCpd(5445));" onmouseout="tooltip.hide();" alt="No structure"></td>
<td><span class="chemname">2-Methyl-1,3-cyclohexanedione</span>; (1193-55-1)</td>
</tr>
<tr>
<td><img style=" width: 50px; " src="/httphandlers/substancetooltip.ashx?id=6805" onmouseover="tooltip.show(jsLoadCpd(6805));" onmouseout="tooltip.hide();" alt="No structure"></td>
<td><span class="chemname">Trifluoromethanesulfonic anhydride</span>; (358-23-6)</td>
</tr>
</tbody>
</table>
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<td style="vertical-align:top;padding-top:5px;padding-bottom:10px;"> Gregory B. Dudley received a B.A. from FSU in 1995 and a Ph.D. in 2000 under the direction of Professor Rick Danheiser at MIT. After completing an
NIH Postdoctoral Fellowship with Professor Samuel Danishefsky at the Sloan-Kettering Institute for Cancer Research, he returned to FSU as an assistant professor in 2002. Professor Dudley was promoted to associate
professor with tenure in 2008. The current mission of his research program is to impact the drug discovery process by contributing fundamental new knowledge in organic synthesis. The addition / fragmentation
methodology featured herein has figured prominently in this effort over the past few years. </td>
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<td style="vertical-align:top;padding-top:5px;padding-bottom:10px;"> Marilda P. Lisboa was born in Rio de Janeiro and raised in Minas Gerais, Brazil. She received her B.S. degree in pharmacy in 2005 and M.S. degree
in pharmaceutical sciences in 2007 from the Federal University of Minas Gerais, Brazil. In 2008, she was awarded a Capes-Fulbright fellowship to pursue her PhD in Chemistry at Florida State University. Currently,
she is a PhD student under the supervision of Professor Gregory Dudley and her research is focused on the synthesis of the natural product palmerolide A. </td>
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<td style="vertical-align:top;padding-top:5px;padding-bottom:10px;"> Tung T. Hoang was born in Ha Long, a small yet beautiful city known for the Ha Long Bay with thousands of islets and its sunshine beach in
northeast Vietnam. Inspired by his high school teacher, Tung entered the chemistry program of Vietnam National University where he earned his B.A. degree in 2006. As a recipient of the Vietnam Education Foundation
Fellowship cohort 2009, he went to Florida State University to pursue his PhD in organic chemistry. Tung is currently working under the direction of Professor Gregory Dudley with interest in the total syntheses of
biologically active natural products. </td>
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<td style="vertical-align:top;padding-top:5px;padding-bottom:10px;"><img src="/content/authors/v88p0353jimmiew.jpg"></td>
<td style="vertical-align:top;padding-top:5px;padding-bottom:10px;"> Jimmie Weaver was born in 1981 in Oklahoma (US). He studied at Southern Nazarene University where he obtained his B.S. degree in chemistry in 2004.
After spending the next year working under William Hildebrand (OUHSC) in an immunology lab, he began his graduate studies at the University of Kansas under the supervision of Jon Tunge. The primary focus of his
graduate work was the synthesis and decarboxylative coupling of a-sulfonyl acetic esters. He completed his Ph.D. in the spring of 2010 and began a post-doctoral fellowship under the direction of Jon Ellman (Yale)
where he is currently working on organocatalysis and drug delivery projects. </td>
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Org. Synth. 2011, 88, 353-363
DOI: 10.15227/orgsyn.088.0353
TANDEM NUCLEOPHILIC ADDITION / FRAGMENTATION OF VINYLOGOUS ACYL TRIFLATES:
2-METHYL-2-(1-OXO-5-HEPTYNYL)-1,3-DITHIANE
Submitted by Marilda P. Lisboa, Tung T. Hoang, and Gregory B. Dudley1.
Checked by Jimmie Weaver and Jonathan Ellman.
1. Procedure
Caution: Exercise care in the handling of trifluoromethanesulfonic anhydride
(corrosive), pyridine (harmful by inhalation), and butyllithium (flammable,
corrosive).
A. 2-Methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one. An oven-dried 2-L,
three-necked, round-bottomed flask equipped with a 1 inch oval magnetic stir
bar, a rubber septum, nitrogen inlet and thermometer is charged with
2-methyl-1,3-cyclohexanedione (15.0 g, 0.115 mol, 1.0 equiv) (Note 1), pyridine
(19.0 mL, 0.230 mol, 2 equiv) (Note 2) and methylene chloride (700 mL) (Note 3).
The reaction mixture is magnetically stirred, cooled at -78 °C for 20 min (Note
4), and trifluoromethanesulfonic anhydride (23.5 mL, 0.138 mol, 1.2 equiv) (Note
1) is added dropwise via syringe over 10 min (Notes 5 and 6). The light yellow
reaction mixture is stirred at -78 °C for 20 min, at 0 °C for 20 min, and at
room temperature for 30 min (Note 4), at which time the reaction mixture is a
homogeneous red solution. The reaction mixture is acidified using 200 mL of a 1M
aqueous solution of hydrochloric acid (Note 7), and the resulting biphasic
solution is transferred to a 2-L separatory funnel. The organic phase is
removed, and the aqueous layer is extracted with diethyl ether (3 x 200 mL)
(Note 8). The organic phases are combined and dried over 100 g of Na2SO4 and
filtered by vacuum suction through a medium porosity fritted glass funnel, and
the solvent is removed under reduced pressure by rotary evaporation (25-45 mmHg,
room temperature water bath) providing the crude product as a red oil (Note 9).
The crude product is purified by chromatography on silica gel (Note 10) to
afford 30.0 g (98%) of the product as a colorless oil (Note 11).
2-Methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one is indefinitely stable
to storage under nitrogen at -13 °C.
B. 2-Methyl-2-(1-oxo-5-heptynyl)-1,3-dithiane. An oven-dried two-necked, 500-mL,
round-bottomed flask equipped with 0.5 inch oval magnetic stir bar, rubber
septum, and a nitrogen inlet adapter is charged with 2-methyl-1,3-dithiane (Note
12) (4.64 mL, 38.7 mmol, 1.1 equiv) and tetrahydrofuran (150 mL) (Note 13). The
resulting solution is cooled at -78 °C (Note 4). A solution of n-butyllithium
(Note 14) (14.5 mL, 35.2 mmol, 1.0 equiv) is added dropwise via syringe over 10
min (Note 15). The light yellow reaction mixture is stirred at -78 °C for 20
min, at 0 °C for 10 min, and at -30 °C for 15 min (Note 4), and then
2-methyl-3-trifluoromethanesulfonyloxy-cyclohex-2-en-1-one (10.0 g, 38.7 mmol,
1.1 equiv) is added dropwise by syringe over 10 min. The light yellow reaction
mixture is stirred at -30 °C for 15 min, at 0 °C for 15 min, and at room
temperature for 30 min (Note 4), at which time the reaction mixture is a
homogeneous red solution (Note 16). A half-saturated solution of aqueous
ammonium chloride (100 mL) (Note 17) is then added and the biphasic solution is
transferred to a 500-mL separatory funnel and extracted with diethyl ether (3 x
50 mL) (Note 8). The organic phases are combined and dried over 70 g of Na2SO4,
filtered by vacuum suction through a medium porosity fritted glass funnel, and
the solvent is removed under reduced pressure by rotary evaporation (25-45 mmHg,
room temperature water bath) providing the crude product as a yellow oil. The
crude product is purified by chromatography on silica gel (Note 18) to afford
6.64 g (71%) (Note 19) of the product as a colorless oil (Note 20).
2. Notes
1. 2-Methyl-1,3-cyclohexanedione (97%) and trifluoromethane-sulfonic anhydride
(99%) were purchased from Sigma-Aldrich and used without further purification.
2. Pyridine (99%) was purchased from Sigma-Aldrich and stored over KOH pellets.
3. Methylene chloride (HPLC Grade) was purchased from Fischer Scientific and
purified using an Innovative Technology solvent purification system.
4. The indicated temperatures at which reaction mixtures are kept refer to the
temperature of external cooling baths as follows: (a) -78 °C cooling bath
prepared with dry ice and acetone, (b) 0 °C cooling bath prepared with ice and
water, and (c) -30 °C cooling bath prepared by adding dry ice to acetone and
carefully monitoring the bath temperature. No external bath was employed for
reactions conducted at room temperature.
5. The highest internal temperature observed by the checkers was -61 °C.
6. The submitters observed that a small amount of white precipitate forms during
the addition of trifluoromethanesulfonic anhydride.
7. Hydrochloric acid (1 M) was prepared by dilution of hydrochloric acid (12.1
M, ACS grade) purchased from EMD Chemicals.
8. Ethyl ether (anhydrous, ACS grade) was purchased from EMD Chemicals and used
without further purification.
9. The submitters obtained a yellow oil.
10. The crude product was purified using 300 g of Silica Gel 60 (Geduran(r)
40-63 µM) wet-loaded as a slurry. The sample was loaded in a minimum volume of
eluent, passed through the column using gradient elution (500 mL of 9:1
hexanes:EtOAc, 500 mL of 8:2 hexanes:EtOAc, and 1000 mL of 7:3 hexanes:EtOAc),
and collected in 20-mL fractions. Fractions 58-99 were collected, combined, and
concentrated under reduced pressure to obtain the final product. The Rf of
2-methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one = 0.62 and
2-methyl-1,3-cyclohexanedione = 0.22 in 8:2 hexanes:ethyl acetate.
11. The compound exhibited the following physical and spectroscopic data: IR
(neat): 2964, 1688, 1416, 1344, 1210, 1135, 1024, 912, 891, 793, 759 cm-1. 1H
NMR pdf(500 MHz, CDCl3) δ: 1.77 (d, J = 1.9 Hz, 3 H), 2.05 - 1.97 (apparent
pentet, 2 H), 2.40 (t, J = 7.9 Hz, 2 H), 2.66 (dtd, J = 6.1, 4.0, 1.9 Hz, 2 H);
13C NMR pdf(126 MHz, CDCl3) δ: 9.0, 20.5, 28.6, 36.5, 118.2 (q, JCF = 319.8 Hz),
127.9, 162.0, 197.5; HRMS (ESI) calcd. for C8H9HF3O4S[M+H]: 259.0246. Found:
259.0246. Anal. calcd. for C8H9F3O4S: C, 37.21; H, 3.51; F, 22.07; S, 12.42.
Found: C, 37.32; H, 3.45; F, 21.84; S, 12.41.
12. 2-Methyl-1,3-dithiane (=98%) was purchased from Fluka and used without
further purification.
13. Tetrahydrofuran (HPLC Grade) was purchased from EMD Chemicals and purified
using an Innovative Technology solvent purification system.
14. n-Butyllithium (2.5 M solution in hexanes) was purchased from Sigma-Aldrich
and titrated using (-)-menthol and 1,10-phenanthroline (= 99%).
15. The internal temperature reached -57 °C during addition.
16. TLC analysis showed formation of product by TLC (Rf (reaction product) =
0.3; Rf (2-methyl-1,3-dithiane) = 0.40, Rf
(2-methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one) = 0.2; elution with
9:1 hexanes:EtOAc; UV and KMnO4/heating visualization). Completion of the
reaction is difficult to discern because n-butyllithium is the limiting reagent,
and therefore both the dithiane and triflate remain even after all of the
butyllithium has been consumed.
17. Half-saturated aqueous ammonium chloride solution was prepared by dilution
of a saturated aqueous ammonium chloride solution; ammonium chloride (99.5% ACS)
reagent purchased from Sigma-Aldrich.
18. The crude product was purified using 300 g of Silica Gel 60 (Geduran(r)
40-63 µM) wet-loaded as a slurry. The sample was loaded in a minimum volume of
eluent, passed through the column using isocratic elution (2000 mL of 98:2
hexanes:EtOAc), and collected in 20-mL fractions. Fractions 38-85 were
collected, combined, and concentrated under reduced pressure to obtain the final
product. The checkers found that excess dithiane complicated isolation of the
product. However, most of the excess dithiane could be easily removed by placing
the unpurified reaction product under high vacuum overnight. The checkers were
then able to isolate the product using 360 g of silica and 3.5 L of 95:5
hexanes:EtOAc. Fractions of 25 mL were collected, and the product was found in
fractions 55-93.
19. The checkers observed that yields were improved substantially using freshly
distilled dithiane (55 °C, 1 mmHg), recently chromatographed triflate that was
concentrated from anhydrous THF, and a newly opened bottle of butyllithium in
hexanes.
20. The compound exhibited the following physical and spectroscopic data: IR
(neat): 2918, 1700, 1446, 1423, 1372, 1359, 1277, 1243, 1217, 1149, 1071, 998,
907, 868, 673 cm-1. 1H NMR pdf(400 MHz, CDCl3) δ: 1.68 (s, 3 H), 1.87 - 1.71 (m,
6 H), 2.14 - 2.04 (m, 1 H), 2.18 (td, J = 6.8, 2.6 Hz, 2 H), 2.62 (dt, J = 7.5,
3.5 Hz, 2 H), 2.79 (t, J = 7.2 Hz, 2 H), 3.10 (t, J = 13.7 Hz, 2 H); 13C NMR
pdf(126 MHz, CDCl3) δ: 3.6, 18.2, 24.1, 24.3, 25.0, 28.2, 34.6, 54.8, 76.5,
78.3, 203.9. HRMS (ESI) calcd. for C12H18HOS2[M+H]: 243.0872. Found: 243.0873.
Anal. calcd. for C12H18OS2: C, 59.46; H, 7.48; S, 26.46. Found: C, 59.48; H,
7.25; S, 26.59. Safety and Waste Disposal Information All hazardous materials
should be handled and disposed of in accordance with "Prudent Practices in the
Laboratory"; National Academy Press; Washington, DC, 1995.
Working with Hazardous Chemicals
The procedures in Organic Syntheses are intended for use only by persons with
proper training in experimental organic chemistry. All hazardous materials
should be handled using the standard procedures for work with chemicals
described in references such as "Prudent Practices in the Laboratory" (The
National Academies Press, Washington, D.C., 2011; the full text can be accessed
free of charge at http://www.nap.edu/catalog.php?record_id=12654). All chemical
waste should be disposed of in accordance with local regulations. For general
guidelines for the management of chemical waste, see Chapter 8 of Prudent
Practices.
In some articles in Organic Syntheses, chemical-specific hazards are highlighted
in red "Caution Notes" within a procedure. It is important to recognize that the
absence of a caution note does not imply that no significant hazards are
associated with the chemicals involved in that procedure. Prior to performing a
reaction, a thorough risk assessment should be carried out that includes a
review of the potential hazards associated with each chemical and experimental
operation on the scale that is planned for the procedure. Guidelines for
carrying out a risk assessment and for analyzing the hazards associated with
chemicals can be found in Chapter 4 of Prudent Practices.
The procedures described in Organic Syntheses are provided as published and are
conducted at one's own risk. Organic Syntheses, Inc., its Editors, and its Board
of Directors do not warrant or guarantee the safety of individuals using these
procedures and hereby disclaim any liability for any injuries or damages claimed
to have resulted from or related in any way to the procedures herein.
The paragraphs above were added in September, 2014. The statements above do not
supersede any specific hazard caution notes and safety instructions included in
the procedure.
3. Discussion
Alkyne building blocks offer many advantages in chemical synthesis owing to
their high enthalpic (chemical potential energy) content and orthogonal
reactivity with respect to other common organic functional groups.2 The advent
of late transition metal catalysts that display a preference for coordination to
π-systems has expanded the scope of alkyne reactions and further increased their
value.3
As the scope of alkyne reactions continues to expand, so too does the demand for
efficient synthetic methods that produce key alkyne building blocks. However,
the energy-rich alkyne π-system is not easy to generate. Functionalized alkynes
are typically prepared using methods that make use of simpler alkyne starting
materials, like acetylide coupling. Common methods for the generation of alkyne
π-bonds from non-acetylenic starting materials include elimination, vinylidene
carbene rearrangement, and fragmentation reactions.4
Vinylogous acyl triflates (VATs) undergo tandem nucleophilic addition /
fragmentation reactions to provide tethered keto-alkynes.5 The overall sequence
achieves the conversion of symmetric, cyclic diones into acyclic alkynyl ketones
that comprise orthogonal and non-contiguous functionalities. The stability of
the triflate anion (an excellent leaving group) enables the fragmentation
process in much the same way as formation of molecular nitrogen is a driving
force in the classic Eschenmoser-Tanabe reaction.6 These mechanistically related
reactions are among the few C-C bond cleaving fragmentations that produce alkyne
π-systems.7
Scheme 1. Alternative strategies for the synthesis of (Z)-6-heneicosen-11-one
The utility of carbanion-triggered fragmentation of vinylogous acyl triflates as
a modern alternative to the Eschenmoser-Tanabe fragmentation is illustrated in
the synthesis of (Z)-6-heneicosen-11-one, the sex pheromone of the Douglas fir
tussock moth (Figure 1). In an earlier approach,8 a cyclic vinylogous methyl
ester was treated with n-decyl Grignard in an addition-hydrolysis sequence to
set up the multi-stage Eschenmoser-Tanabe process. Using the current method,
nucleophilic addition of the same Grignard reagent to the corresponding
vinylogous triflate triggered fragmentation directly.9 The streamlined entry
into the fragmentation pathway provides an increased overall yield in fewer
steps, and it avoids acidic conditions and the sometimes-troublesome preparation
of cyclic enone oxides.6b
The scope of appropriate nucleophiles is illustrated in Table 1. Carbanion
reagents were the first nucleophiles to be explored,5 as these provide alkyl and
aryl ketones of the type most closely associated with the Eschenmoser-Tanabe
fragmentation (entries 1-4, 10-12). The typical reaction is conducted by
treating the nucleophile with the vinylogous acyl triflate in THF at low
temperature to achieve the initial 1,2-addition, and then warming the reaction
mixture to room temperature or above to promote the (entropically favorable)
fragmentation event. It has been observed experimentally that addition /
fragmentation reactions using unstabilized
Table 1. Scope of the addition/fragmentation reaction
alkyllithium and alkyl Grignard reagents occur more efficiently in toluene than
in THF (entry 2);9 this observation may be attributable to solvent-dependent
aggregation states of the organometallic reagent. In toluene, higher aggregation
states of the nucleophile likely attenuate its reactivity and promote
selectivity for the desired 1,2-addition over alternative pathways like proton-
or electron-transfer.
Addition of stabilized carbanion nucleophiles to vinylogous acyl triflates
triggers what we term the VAT-Claisen10 reaction: a ring-opening fragmentation
to give acyclic β-keto ester and related products much like those observed
traditionally in the Claisen condensation (entries 5-6). Whereas the Claisen
condensation is driven by deprotonation of final product, the VAT-Claisen
reaction is rendered irreversible by the fragmentation event. Deprotonation of
the final VAT-Claisen product may still occur incidentally, in which case the
use of excess nucleophile is required to realize complete conversion (entry 5).
Other suitable nucleophiles for promoting fragmentation include primary lithium
amides (entry 7) and lithium triethylborohydride (entry 8).5 Diisobutylaluminum
hydride reduces the VAT carbonyl but does not trigger fragmentation; the
resulting alcohol can then be treated with excess Grignard reagents to promote
fragmentation and in situ trapping of the resultant aldehyde (entry 9).11 Other
suitable VAT substrates are shown in entries 10-12. The five- and seven-membered
ring VATs are less stable than their hexacyclic counterparts, and as such they
are best prepared immediately prior to use.
The tandem nucleophilic addition / fragmentation of cyclic VAT substrates
provides an alternative entry into the classic Eschenmoser-Tanabe pathway, one
of the few Grob-type fragmentations capable of generating alkyne π-bonds. The
method outlined above delivers orthogonally functionalized acyclic building
blocks - alkynyl ketones and related compounds - from symmetrical cyclic dione
starting materials. This methodology continues to evolve; application to the
synthesis of natural products,12 homopropargyl alcohol13 and homopropargyl
amine14 derivatives from heterocyclic VATs, and other challenging classes of
organic compounds15 are underway at this time.
--------------------------------------------------------------------------------
References and Notes
1. Department of Chemistry and Biochemistry, Florida State University,
Tallahassee, FL 32306-4390, USA. E-Mail: gdudley@chem.fsu.edu This work was
supported by a grant from the National Science Foundation (NSF-CHE
0749918). M.P.L. is a recipient of the Capes-Fulbright Graduate Research
Fellowship (2008). T.T.H. is a recipient of the Vietnam Education
Foundation (VEF) Graduate Fellowship (2009).
2. All-Carbon Functions Polyynes, Arynes, Enynes, and Alkynes. In Science of
Synthesis: Houben-Weyl Methods of Molecular Transformation; Thomas, E. J.,
Hopf, H., Eds., Thieme: Stuttgart, 2008; Vol. 43.
3. (a) Tsuji, J. Transition Metal Reagents and Catalysts: Innovations in
Organic Synthesis; Wiley & Sons: New York, 2000. (b) Lewis Acids in Organic
Synthesis; Yamamoto, H., Ed.; Wiley-VCH: New York, 2000.
4. (a) Larock, R. C. Comprehensive Organic Transformations, 2nd Ed.; Wiley &
Sons: New York, 1999; pp 563-583. (b) Brandsma, L. Preparative Acetylenic
Chemistry, 2nd Ed.; Elsevier: Amsterdam, 1988.
5. (a) Kamijo, S.; Dudley, G. B. J. Am. Chem. Soc. 2005, 127,
5028-5029.[CrossRef] (b) Kamijo, S.; Dudley, G. B. J. Am. Chem. Soc. 2006,
128, 6499-6507; Addition/Correction: J. Am. Chem. Soc. 2010, 132,
8223.[CrossRef]
6. (a) Eschenmoser, A.; Felix, D.; Ohloff, G. Helv. Chim. Acta 1967, 50,
708-713.[CrossRef] (b) Tanabe, M.; Crowe, D. F.; Dehn, R. L. Tetrahedron
Lett. 1967, 3943-3946.[CrossRef] (c) Grob, C. A.; Schiess, P. W. H. Angew.
Chem., Int. Ed. Engl. 1967, 6, 1-15.[CrossRef] (d) Weyerstahl, P.;
Marschall, H. In Comprehensive Organic Synthesis, Trost, B. M., Fleming,
I., Eds.; Pergamon Press: Elmsford, NY, 1991; Vol. 6, pp
1041-1070.[CrossRef] (e) Prantz, K.; Mulzer, J. Chem. Rev. 2010, 110,
3741-3766.[CrossRef]
7. (a) For an early example driven by formation of carbon dioxide, see: Grob,
C. A.; Csapilla, J. Cseh, G. Helv. Chim. Acta 1964, 47,
1590-1602.[CrossRef] (b) For recent examples driven by formation of
molecular nitrogen, see: Draghici, C.; Brewer, M. J. Am. Chem. Soc. 2008,
130, 3766-3767;[CrossRef] (c) Draghici, C.; Huang, Q.; Brewer, M. J. Org.
Chem. 2009, 74, 8410-8413;[CrossRef] (d) Bayir, A.; Draghici, C.; Brewer,
M. J. Org. Chem. 2010, 75, 296-302.[CrossRef]
8. Kocienski, P. J.; Cernigliaro, G. J. J. Org. Chem. 1976, 41,
2927-2928.[CrossRef]
9. Jones, D. M.; Kamijo, S.; Dudley, G. B. Synlett 2006, 936-938.
10. (a) Kamijo, S.; Dudley, G. B. Org. Lett. 2006, 8, 175-177.[CrossRef] (b)
Jones, D. M.; Lisboa, M. P.; Kamijo, S.; Dudley, G. B. J. Org. Chem. 2010,
75, 3260-3267.[CrossRef]
11. Kamijo, S.; Dudley, G. B. Tetrahedron Lett. 2006, 47, 5629-5632.[CrossRef]
12. Jones, D. M.; Dudley, G. B. Synlett 2010, 223-226.
13. Tummatorn, J.; Dudley, G. B. J. Am. Chem. Soc. 2008, 130,
5050-5051.[CrossRef]
14. Tummatorn, J.; Dudley, G. B. Org. Lett. 2011, 13, 158-160.[CrossRef]
15. Jones, D. M.; Dudley, G. B. Tetrahedron 2010, 66, 4860-4866.[CrossRef]
--------------------------------------------------------------------------------
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
2-Methyl-2-(1-oxo-5-heptynyl)-1,3-dithiane: 5-Heptyn-1-one,
1-(2-methyl-1,3-dithian-2-yl)-; (892874-94-1)
2-Methyl-1,3-dithiane; (6007-26-7)
n-Butyllithium; (109-72-8)
2-Methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one: Methanesulfonic acid,
1,1,1-trifluoro-, 2-methyl-3-oxo-1-cyclohexen-1-yl ester; (150765-78-9)
2-Methyl-1,3-cyclohexanedione; (1193-55-1)
Trifluoromethanesulfonic anhydride; (358-23-6)
Gregory B. Dudley received a B.A. from FSU in 1995 and a Ph.D. in 2000 under the
direction of Professor Rick Danheiser at MIT. After completing an NIH
Postdoctoral Fellowship with Professor Samuel Danishefsky at the Sloan-Kettering
Institute for Cancer Research, he returned to FSU as an assistant professor in
2002. Professor Dudley was promoted to associate professor with tenure in 2008.
The current mission of his research program is to impact the drug discovery
process by contributing fundamental new knowledge in organic synthesis. The
addition / fragmentation methodology featured herein has figured prominently in
this effort over the past few years. Marilda P. Lisboa was born in Rio de
Janeiro and raised in Minas Gerais, Brazil. She received her B.S. degree in
pharmacy in 2005 and M.S. degree in pharmaceutical sciences in 2007 from the
Federal University of Minas Gerais, Brazil. In 2008, she was awarded a
Capes-Fulbright fellowship to pursue her PhD in Chemistry at Florida State
University. Currently, she is a PhD student under the supervision of Professor
Gregory Dudley and her research is focused on the synthesis of the natural
product palmerolide A. Tung T. Hoang was born in Ha Long, a small yet beautiful
city known for the Ha Long Bay with thousands of islets and its sunshine beach
in northeast Vietnam. Inspired by his high school teacher, Tung entered the
chemistry program of Vietnam National University where he earned his B.A. degree
in 2006. As a recipient of the Vietnam Education Foundation Fellowship cohort
2009, he went to Florida State University to pursue his PhD in organic
chemistry. Tung is currently working under the direction of Professor Gregory
Dudley with interest in the total syntheses of biologically active natural
products. Jimmie Weaver was born in 1981 in Oklahoma (US). He studied at
Southern Nazarene University where he obtained his B.S. degree in chemistry in
2004. After spending the next year working under William Hildebrand (OUHSC) in
an immunology lab, he began his graduate studies at the University of Kansas
under the supervision of Jon Tunge. The primary focus of his graduate work was
the synthesis and decarboxylative coupling of a-sulfonyl acetic esters. He
completed his Ph.D. in the spring of 2010 and began a post-doctoral fellowship
under the direction of Jon Ellman (Yale) where he is currently working on
organocatalysis and drug delivery projects.
Copyright © 1921-2024, Organic Syntheses, Inc. All Rights Reserved
NOTES
1. 2-Methyl-1,3-cyclohexanedione (97%) and trifluoromethane-sulfonic anhydride
(99%) were purchased from Sigma-Aldrich and used without further purification.
2. Pyridine (99%) was purchased from Sigma-Aldrich and stored over KOH pellets.
3. Methylene chloride (HPLC Grade) was purchased from Fischer Scientific and
purified using an Innovative Technology solvent purification system.
4. The indicated temperatures at which reaction mixtures are kept refer to the
temperature of external cooling baths as follows: (a) -78 °C cooling bath
prepared with dry ice and acetone, (b) 0 °C cooling bath prepared with ice and
water, and (c) -30 °C cooling bath prepared by adding dry ice to acetone and
carefully monitoring the bath temperature. No external bath was employed for
reactions conducted at room temperature.
5. The highest internal temperature observed by the checkers was -61 °C.
6. The submitters observed that a small amount of white precipitate forms during
the addition of trifluoromethanesulfonic anhydride.
7. Hydrochloric acid (1 M) was prepared by dilution of hydrochloric acid (12.1
M, ACS grade) purchased from EMD Chemicals.
8. Ethyl ether (anhydrous, ACS grade) was purchased from EMD Chemicals and used
without further purification.
9. The submitters obtained a yellow oil.
10. The crude product was purified using 300 g of Silica Gel 60 (Geduran(r)
40-63 µM) wet-loaded as a slurry. The sample was loaded in a minimum volume of
eluent, passed through the column using gradient elution (500 mL of 9:1
hexanes:EtOAc, 500 mL of 8:2 hexanes:EtOAc, and 1000 mL of 7:3 hexanes:EtOAc),
and collected in 20-mL fractions. Fractions 58-99 were collected, combined, and
concentrated under reduced pressure to obtain the final product. The Rf of
2-methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one = 0.62 and
2-methyl-1,3-cyclohexanedione = 0.22 in 8:2 hexanes:ethyl acetate.
11. The compound exhibited the following physical and spectroscopic data: IR
(neat): 2964, 1688, 1416, 1344, 1210, 1135, 1024, 912, 891, 793, 759 cm-1. 1H
NMR pdf(500 MHz, CDCl3) δ: 1.77 (d, J = 1.9 Hz, 3 H), 2.05 - 1.97 (apparent
pentet, 2 H), 2.40 (t, J = 7.9 Hz, 2 H), 2.66 (dtd, J = 6.1, 4.0, 1.9 Hz, 2 H);
13C NMR pdf(126 MHz, CDCl3) δ: 9.0, 20.5, 28.6, 36.5, 118.2 (q, JCF = 319.8 Hz),
127.9, 162.0, 197.5; HRMS (ESI) calcd. for C8H9HF3O4S[M+H]: 259.0246. Found:
259.0246. Anal. calcd. for C8H9F3O4S: C, 37.21; H, 3.51; F, 22.07; S, 12.42.
Found: C, 37.32; H, 3.45; F, 21.84; S, 12.41.
12. 2-Methyl-1,3-dithiane (=98%) was purchased from Fluka and used without
further purification.
13. Tetrahydrofuran (HPLC Grade) was purchased from EMD Chemicals and purified
using an Innovative Technology solvent purification system.
14. n-Butyllithium (2.5 M solution in hexanes) was purchased from Sigma-Aldrich
and titrated using (-)-menthol and 1,10-phenanthroline (= 99%).
15. The internal temperature reached -57 °C during addition.
16. TLC analysis showed formation of product by TLC (Rf (reaction product) =
0.3; Rf (2-methyl-1,3-dithiane) = 0.40, Rf
(2-methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one) = 0.2; elution with
9:1 hexanes:EtOAc; UV and KMnO4/heating visualization). Completion of the
reaction is difficult to discern because n-butyllithium is the limiting reagent,
and therefore both the dithiane and triflate remain even after all of the
butyllithium has been consumed.
17. Half-saturated aqueous ammonium chloride solution was prepared by dilution
of a saturated aqueous ammonium chloride solution; ammonium chloride (99.5% ACS)
reagent purchased from Sigma-Aldrich.
18. The crude product was purified using 300 g of Silica Gel 60 (Geduran(r)
40-63 µM) wet-loaded as a slurry. The sample was loaded in a minimum volume of
eluent, passed through the column using isocratic elution (2000 mL of 98:2
hexanes:EtOAc), and collected in 20-mL fractions. Fractions 38-85 were
collected, combined, and concentrated under reduced pressure to obtain the final
product. The checkers found that excess dithiane complicated isolation of the
product. However, most of the excess dithiane could be easily removed by placing
the unpurified reaction product under high vacuum overnight. The checkers were
then able to isolate the product using 360 g of silica and 3.5 L of 95:5
hexanes:EtOAc. Fractions of 25 mL were collected, and the product was found in
fractions 55-93.
19. The checkers observed that yields were improved substantially using freshly
distilled dithiane (55 °C, 1 mmHg), recently chromatographed triflate that was
concentrated from anhydrous THF, and a newly opened bottle of butyllithium in
hexanes.
20. The compound exhibited the following physical and spectroscopic data: IR
(neat): 2918, 1700, 1446, 1423, 1372, 1359, 1277, 1243, 1217, 1149, 1071, 998,
907, 868, 673 cm-1. 1H NMR pdf(400 MHz, CDCl3) δ: 1.68 (s, 3 H), 1.87 - 1.71 (m,
6 H), 2.14 - 2.04 (m, 1 H), 2.18 (td, J = 6.8, 2.6 Hz, 2 H), 2.62 (dt, J = 7.5,
3.5 Hz, 2 H), 2.79 (t, J = 7.2 Hz, 2 H), 3.10 (t, J = 13.7 Hz, 2 H); 13C NMR
pdf(126 MHz, CDCl3) δ: 3.6, 18.2, 24.1, 24.3, 25.0, 28.2, 34.6, 54.8, 76.5,
78.3, 203.9. HRMS (ESI) calcd. for C12H18HOS2[M+H]: 243.0872. Found: 243.0873.
Anal. calcd. for C12H18OS2: C, 59.46; H, 7.48; S, 26.46. Found: C, 59.48; H,
7.25; S, 26.59. Safety and Waste Disposal Information All hazardous materials
should be handled and disposed of in accordance with "Prudent Practices in the
Laboratory"; National Academy Press; Washington, DC, 1995.
REFERENCES/ENDNOTES
1. Department of Chemistry and Biochemistry, Florida State University,
Tallahassee, FL 32306-4390, USA. E-Mail: gdudley@chem.fsu.edu This work was
supported by a grant from the National Science Foundation (NSF-CHE
0749918). M.P.L. is a recipient of the Capes-Fulbright Graduate Research
Fellowship (2008). T.T.H. is a recipient of the Vietnam Education
Foundation (VEF) Graduate Fellowship (2009).
2. All-Carbon Functions Polyynes, Arynes, Enynes, and Alkynes. In Science of
Synthesis: Houben-Weyl Methods of Molecular Transformation; Thomas, E. J.,
Hopf, H., Eds., Thieme: Stuttgart, 2008; Vol. 43.
3. (a) Tsuji, J. Transition Metal Reagents and Catalysts: Innovations in
Organic Synthesis; Wiley & Sons: New York, 2000. (b) Lewis Acids in Organic
Synthesis; Yamamoto, H., Ed.; Wiley-VCH: New York, 2000.
4. (a) Larock, R. C. Comprehensive Organic Transformations, 2nd Ed.; Wiley &
Sons: New York, 1999; pp 563-583. (b) Brandsma, L. Preparative Acetylenic
Chemistry, 2nd Ed.; Elsevier: Amsterdam, 1988.
5. (a) Kamijo, S.; Dudley, G. B. J. Am. Chem. Soc. 2005, 127,
5028-5029.[CrossRef] (b) Kamijo, S.; Dudley, G. B. J. Am. Chem. Soc. 2006,
128, 6499-6507; Addition/Correction: J. Am. Chem. Soc. 2010, 132,
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6. (a) Eschenmoser, A.; Felix, D.; Ohloff, G. Helv. Chim. Acta 1967, 50,
708-713.[CrossRef] (b) Tanabe, M.; Crowe, D. F.; Dehn, R. L. Tetrahedron
Lett. 1967, 3943-3946.[CrossRef] (c) Grob, C. A.; Schiess, P. W. H. Angew.
Chem., Int. Ed. Engl. 1967, 6, 1-15.[CrossRef] (d) Weyerstahl, P.;
Marschall, H. In Comprehensive Organic Synthesis, Trost, B. M., Fleming,
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1041-1070.[CrossRef] (e) Prantz, K.; Mulzer, J. Chem. Rev. 2010, 110,
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7. (a) For an early example driven by formation of carbon dioxide, see: Grob,
C. A.; Csapilla, J. Cseh, G. Helv. Chim. Acta 1964, 47,
1590-1602.[CrossRef] (b) For recent examples driven by formation of
molecular nitrogen, see: Draghici, C.; Brewer, M. J. Am. Chem. Soc. 2008,
130, 3766-3767;[CrossRef] (c) Draghici, C.; Huang, Q.; Brewer, M. J. Org.
Chem. 2009, 74, 8410-8413;[CrossRef] (d) Bayir, A.; Draghici, C.; Brewer,
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9. Jones, D. M.; Kamijo, S.; Dudley, G. B. Synlett 2006, 936-938.
10. (a) Kamijo, S.; Dudley, G. B. Org. Lett. 2006, 8, 175-177.[CrossRef] (b)
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ARTICLE COMPOUNDS
2-Methyl-2-(1-oxo-5-heptynyl)-1,3-dithiane: 5-Heptyn-1-one,
1-(2-methyl-1,3-dithian-2-yl)-; (892874-94-1)2-Methyl-1,3-dithiane;
(6007-26-7)n-Butyllithium;
(109-72-8)2-Methyl-3-trifluoromethansulfonyloxy-cyclohex-2-en-1-one:
Methanesulfonic acid, 1,1,1-trifluoro-, 2-methyl-3-oxo-1-cyclohexen-1-yl ester;
(150765-78-9)2-Methyl-1,3-cyclohexanedione; (1193-55-1)Trifluoromethanesulfonic
anhydride; (358-23-6)
AUTHORS
Gregory B. Dudley received a B.A. from FSU in 1995 and a Ph.D. in 2000 under the
direction of Professor Rick Danheiser at MIT. After completing an NIH
Postdoctoral Fellowship with Professor Samuel Danishefsky at the Sloan-Kettering
Institute for Cancer Research, he returned to FSU as an assistant professor in
2002. Professor Dudley was promoted to associate professor with tenure in 2008.
The current mission of his research program is to impact the drug discovery
process by contributing fundamental new knowledge in organic synthesis. The
addition / fragmentation methodology featured herein has figured prominently in
this effort over the past few years. Marilda P. Lisboa was born in Rio de
Janeiro and raised in Minas Gerais, Brazil. She received her B.S. degree in
pharmacy in 2005 and M.S. degree in pharmaceutical sciences in 2007 from the
Federal University of Minas Gerais, Brazil. In 2008, she was awarded a
Capes-Fulbright fellowship to pursue her PhD in Chemistry at Florida State
University. Currently, she is a PhD student under the supervision of Professor
Gregory Dudley and her research is focused on the synthesis of the natural
product palmerolide A. Tung T. Hoang was born in Ha Long, a small yet beautiful
city known for the Ha Long Bay with thousands of islets and its sunshine beach
in northeast Vietnam. Inspired by his high school teacher, Tung entered the
chemistry program of Vietnam National University where he earned his B.A. degree
in 2006. As a recipient of the Vietnam Education Foundation Fellowship cohort
2009, he went to Florida State University to pursue his PhD in organic
chemistry. Tung is currently working under the direction of Professor Gregory
Dudley with interest in the total syntheses of biologically active natural
products. Jimmie Weaver was born in 1981 in Oklahoma (US). He studied at
Southern Nazarene University where he obtained his B.S. degree in chemistry in
2004. After spending the next year working under William Hildebrand (OUHSC) in
an immunology lab, he began his graduate studies at the University of Kansas
under the supervision of Jon Tunge. The primary focus of his graduate work was
the synthesis and decarboxylative coupling of a-sulfonyl acetic esters. He
completed his Ph.D. in the spring of 2010 and began a post-doctoral fellowship
under the direction of Jon Ellman (Yale) where he is currently working on
organocatalysis and drug delivery projects.