{"id":6302,"date":"2015-08-26T12:33:05","date_gmt":"2015-08-26T04:33:05","guid":{"rendered":"\/\/www.gsbet888.com\/?p=6302"},"modified":"2019-08-02T18:55:15","modified_gmt":"2019-08-02T10:55:15","slug":"%e4%b8%b9%e5%b0%bc%e8%b0%a2%e5%a4%ab%e6%96%af%e5%9f%ba-%e5%8c%97%e5%8e%9f%e5%8f%8c%e7%83%afdanishefsky-kitahara-diene","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/reactions\/2015\/08\/%e4%b8%b9%e5%b0%bc%e8%b0%a2%e5%a4%ab%e6%96%af%e5%9f%ba-%e5%8c%97%e5%8e%9f%e5%8f%8c%e7%83%afdanishefsky-kitahara-diene.html","title":{"rendered":"\u4e39\u5c3c\u8c22\u592b\u65af\u57fa-\u5317\u539f\u53cc\u70ef(Danishefsky-Kitahara Diene)"},"content":{"rendered":"<h4>\u6982\u8981<\/h4>\n<p>siloxydiene\u4fd7\u79f0<strong>Danishefsky(-\u5317\u539f)\u53cc\u70ef<\/strong>\uff0c\u662f\u4e00\u79cd\u6709\u673a\u7845\u5316\u5408\u7269\u3002\u5176\u7cfb\u7edf\u540d\u79f0\u662f\u53cd-1-\u7532\u6c27\u57fa-3-(\u4e09\u7532\u57fa\u7845\u6c27\u57fa)-1,3-\u4e01\u4e8c\u70ef\u3002\u8be5\u53cc\u70ef\u7531\u4e8e\u6709\u4e24\u4e2a\u4f9b\u7535\u53d6\u4ee3\u57fa\uff0c\u6240\u4ee5HOMO\u7684\u80fd\u7ea7\u6bd4\u8f83\u9ad8\uff0c\u5f88\u5bb9\u6613\u4e0e\u7f3a\u7535\u5b50\u5e95\u7269\u53d1\u751f<a href=\"http:\/\/www.chem-station.com\/odos\/2009\/06\/diels-alder.html\">Diels-Alder\u53cd\u5e94<\/a>\u6216<a href=\"http:\/\/www.chem-station.com\/odos\/2009\/07\/diels-alder-hetero-diels-alder.html\">\u6742\u73afDiels-Alder\u53cd\u5e94<\/a><\/p>\n<p>&nbsp;<\/p>\n<h4>\u57fa\u672c\u6587\u732e<\/h4>\n<ul>\n<li>Danishefsky, S. J.; Kitahara, T. <em>J. Am. Chem. Soc.<\/em> <strong>1974<\/strong>,\u00a0<em>96<\/em>, 7807. doi:<a href=\"http:\/\/dx.doi.org\/10.1021\/ja00832a031\">10.1021\/ja00832a031<\/a><\/li>\n<li>Danishefsky, S. J.; Hirama, M.; Gombatz, K.; Harayama, T.; Berman,\u00a0E.; Schuda, P. <em>J. Am. Chem. Soc.<\/em> <strong>1978<\/strong>, <em>100<\/em>,\u00a06536. DOI: <a href=\"http:\/\/dx.doi.org\/10.1021\/ja00488a063\">10.1021\/ja00488a063<\/a><\/li>\n<li>Danishefsky, S. J. <em>Acc. Chem. Res.<\/em> <strong>1981<\/strong>,<em>14<\/em>, 400. DOI: <a href=\"http:\/\/dx.doi.org\/10.1021\/ar00072a006\">10.1021\/ar00072a006<\/a><\/li>\n<li>Danishefsky, S. J.; Kitahara, T.; Shuda, P. F. <em>Org. Synth.\u00a0<\/em><strong>1983<\/strong>, <em>61<\/em>, 147. [website]<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n<h4>\u53cd\u5e94\u673a\u7406<\/h4>\n<p>&nbsp;<\/p>\n<h4>\u53cd\u5e94\u5b9e\u4f8b<\/h4>\n<p>&nbsp;<\/p>\n<h4>\u5b9e\u9a8c\u6b65\u9aa4<\/h4>\n<p>Danishefsky\u53cc\u70ef\u7684\u5236\u5907\u65b9\u6cd5[1]\n<blockquote><p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2015\/08\/danishefsky_diene_2.gif\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-6304 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2015\/08\/danishefsky_diene_2.gif\" alt=\"danishefsky_diene_2\" width=\"315\" height=\"129\" \/><\/a>\u5728\u914d\u5907\u6709\u673a\u68b0\u6405\u62cc\u5668\u7684\u4e09\u9888\u5706\u5e95\u70e7\u74f6\u4e2d\uff0c\u52a0\u5165\u4e09\u4e59\u80fa (575g, 5.7mol)\u3001\u65e0\u6c34ZnCl2(10.0g, 0.07\u00a0mol),\u5728\u6c2e\u6c14\u4fdd\u62a4\u4e0b\u6405\u62cc1\u5c0f\u65f6\u3002\u7136\u540e\u5728\u8be5\u6df7\u5408\u6eb6\u6db2\u4e2d\u52a0\u51654-methoxy-3-buten-2-one (250g, 2.50mol)\u7684\u82ef(750 mL)\u6eb6\u6db2\u3002\u6405\u62cc5\u5206\u949f\u540e\uff0c\u8fc5\u901f\u52a0\u5165TMSCl(542g, 5.0 mol)\u3002\u53cd\u5e94\u6db2\u6700\u521d\u5148\u53d8\u6210\u7c89\u8272\uff0c\u7136\u540e\u6e10\u6e10\u5730\u53d8\u6210\u7ea2\u8272\uff0c\u6700\u7ec8\u53d8\u6210\u8336\u8272\u3002\u7136\u540e\u5728\u51b0\u6d74\u4e0b\u51b7\u5374\u523045\u2103\uff0c\u5e76\u4e14\u4fdd\u6301\u5728\u8fd9\u4e2a\u6e29\u5ea6\u6405\u62cc12\u5c0f\u65f6\u3002\u968f\u7740\u53cd\u5e94\u7684\u8fdb\u884c\uff0c\u6eb6\u6db2\u7684\u5e74\u5ea6\u4e0d\u65ad\u53d8\u5927\u3002\u53cd\u5e94\u5b8c\u6bd5\u51b7\u5374\u5bfc\u5e08\u95ee\uff0c\u52a0\u5165\u4e59\u919a(5L)\u3002\u7528\u7802\u82af\u6f0f\u6597\u6ee4\u53bb\u56fa\u4f53\uff0c\u5e76\u4e14\u518d\u7528\u4e59\u919a\u6d17\u51c0\u3002\u5f97\u5230\u7684\u6eb6\u6db2\u65cb\u84b8\u6d53\u7f29\u540e\u6700\u7ec8\u5f97\u5230\u6709\u751c\u5473\u7684\u6cb9\u72b6\u7269\u8d28\u3002\u8f6c\u79fb\u52301L\u7684\u5bb9\u5668\u4e2d\uff0c\u7528Vigreux column\u51cf\u538b\u84b8\u998f\u7eaf\u5316\u3002\u521d\u998f\u5206\u6742\u8d28\u572870\uff5e78\u2103(22mmHg)\u6d41\u51fa\u9664\u53bb\uff0c\u63a5\u7740\u572878\uff5e81\u2103\u6d41\u51fa\u7684\u662f\u76ee\u6807\u4ea7\u7269(245g)\uff0c\u4f46\u662f\u5176\u4e2d\u6df7\u67095-10\uff05\u539f\u6599\uff0c\u4f46\u662f\u4f7f\u7528\u8fdb\u884c\u6240\u9700\u53cd\u5e94\u5df2\u7ecf\u8db3\u591f\u3002\u5f53\u7136\u4e5f\u53ef\u4ee5\u8fdb\u884c\u518d\u6b21\u51cf\u538b\u84b8\u998f\u5f97\u5230\u7eaf\u5ea6\u66f4\u9ad8\u7684\u4ea7\u7269<em>trans<\/em>-1-methoxy-3-trimethylsiloxy-1,3-butadiene(200g,\u4ea7\u738746%)\u3002<\/p>\n<p>&nbsp;<\/p><\/blockquote>\n<h4>\u5b9e\u9a8c\u6280\u5de7<\/h4>\n<p>\u203bZnCl2\u6700\u597d\u4e8b\u5148\u5e72\u71e5\u9664\u53bb\u6c34\u5206\uff0c\u518d\u4f7f\u7528\u3002<\/p>\n<p>&nbsp;<\/p>\n<h4>\u53c2\u8003\u6587\u732e<\/h4>\n[1] Danishefsky, S. J.; Kitahara, T.; Shuda, P. F. <em>Org. Synth. \u00a0<\/em><strong>1983<\/strong>, <em>61<\/em>, 147. [website]\n<p>&nbsp;<\/p>\n<p><strong>\u672c\u6587\u7248\u6743\u5c5e\u4e8e\u00a0<a href=\"\/\/www.gsbet888.com\/\">Chem-Station\u5316\u5b66\u7a7a\u95f4<\/a>\uff0c \u6b22\u8fce\u70b9\u51fb\u6309\u94ae\u5206\u4eab\uff0c\u672a\u7ecf\u8bb8\u53ef\uff0c\u8c22\u7edd\u8f6c\u8f7d<\/strong> <\/p>\n","protected":false},"excerpt":{"rendered":"\u6982\u8981 siloxydiene\u4fd7\u79f0Danishefsky(-\u5317\u539f)\u53cc\u70ef\uff0c\u662f\u4e00\u79cd\u6709\u673a\u7845\u5316\u5408\u7269\u3002\u5176\u7cfb\u7edf\u540d\u79f0\u662f\u53cd-1-\u7532\u6c27\u57fa-3-(\u4e09\u7532\u57fa\u7845\u6c27\u57fa)-1,3-\u4e01\u4e8c\u70ef\u3002\u8be5\u53cc\u70ef\u7531\u4e8e\u6709\u4e24\u4e2a\u4f9b\u7535\u53d6\u4ee3\u57fa\uff0c\u6240\u4ee5HOMO\u7684\u80fd\u7ea7\u6bd4\u8f83\u9ad8\uff0c\u5f88\u5bb9\u6613\u4e0e\u7f3a\u7535\u5b50\u5e95\u7269\u53d1\u751fDiels-Alder\u53cd\u5e94\u6216\u6742\u73afDiels-Alder\u53cd\u5e94 &nbsp; \u57fa\u672c\u6587\u732e Danishefsky, S. J.; Kitahara, T. J. Am. Chem. Soc. 1974,\u00a096, 7807. doi:10.1021\/ja00832a031 Danishefsky, S. J.; Hirama, M.; Gombatz, K.; Harayama, T.; Berman,\u00a0E.; Schuda, P. J. Am. Chem. Soc. 1978, 100,\u00a06536. DOI: 10.1021\/ja00488a063 Danishefsky, S. J. Acc. Chem. Res. 1981,14, 400. DOI: 10.1021\/ar00072a006 Danishefsky, S. J.; Kitahara, T.; Shuda, P. F. Org. Synth.\u00a01983, 61, 147. 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J.; Kitahara, T.; Shuda, P. F. Org. Synth. \u00a01983, 61, 147. 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