{"id":652,"date":"2014-03-16T20:42:50","date_gmt":"2014-03-16T12:42:50","guid":{"rendered":"\/\/www.gsbet888.com\/?p=652"},"modified":"2019-08-02T18:57:14","modified_gmt":"2019-08-02T10:57:14","slug":"%e5%ba%93%e5%b0%94%e6%8f%90%e6%96%af%e9%87%8d%e6%8e%92%e5%8f%8d%e5%ba%94curtius-rearrangement-reaction","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/reactions\/2014\/03\/%e5%ba%93%e5%b0%94%e6%8f%90%e6%96%af%e9%87%8d%e6%8e%92%e5%8f%8d%e5%ba%94curtius-rearrangement-reaction.html","title":{"rendered":"\u5e93\u5c14\u63d0\u65af\u91cd\u6392\u53cd\u5e94(Curtius Rearrangement Reaction)"},"content":{"rendered":"<p>&nbsp;<\/p>\n<ul>\n<li><strong>\u6982\u8981<\/strong><\/li>\n<\/ul>\n<p>\u4ee5\u9178\u6216\u8005\u9170\u5364\u4f5c\u4e3a\u53cd\u5e94\u5e95\u7269\uff0c\u5f15\u53d1\u5f62\u6210\u7684\u9170\u57fa\u53e0\u6c2e\u4e2d\u95f4\u4f53\u5728\u52a0\u70ed\u6761\u4ef6\u4e0b\u91cd\u6392\uff0c\u5f62\u6210\u5f02\u6c30\u9178\u916f\u3002\u5982\u679c\u6b64\u65f6\uff0c\u6709\u6c34\u4ecb\u5165\u53cd\u5e94\u7684\u8bdd\uff0c\u5f02\u6c30\u9178\u916f\u4f1a\u7acb\u5373\u52a0\u6c34\u5206\u89e3\uff0c\u5f62\u6210\u8131\u6389\u4e00\u4e2a\u78b3\u7684\u80fa\u3002\u6b64\u5916\uff0c\u8be5\u65b9\u6cd5\u662f\u4e3a\u6570\u4e0d\u591a\u7684\u3001\u80fd\u591f\u5408\u6210\u5177\u6709\u5149\u5b66\u6d3b\u6027\u7684\u94fe\u72b6\u80fa\u7684\u65b9\u6cd5\u4e4b\u4e00\u3002<\/p>\n<p>\u9664\u4e86\u6c34\u4ee5\u5916\uff0c\u5982\u679c\u4f7f\u7528\u4e00\u4e9b\u9002\u5f53\u7684\u9187\u4f5c\u4e3a\u53cd\u5e94\u5242\u7684\u8bdd\uff0c\uff0c\u5c31\u53ef\u4ee5\u5f88\u65b9\u4fbf\u7684\u5f62\u6210\u5404\u79cd\u6c28\u57fa\u9178\u916f\u7c7b\u57fa\u56e2\u4f5c\u4e3a\u80fa\u57fa\u7684\u4fdd\u62a4\u57fa\uff0c\u6bd4\u5982Boc\u3001Cbz\u7b49\u3002\u56e0\u6b64\uff0c\u6b64\u53cd\u5e94\u662f\u5e94\u7528\u6027\u6781\u5176\u9ad8\u7684\u4e00\u4e2a\u91cd\u6392\u53cd\u5e94\u3002<\/p>\n<p>\u53e0\u6c2e\u94a0\u5177\u6709\u4e00\u5b9a\u7684\u7206\u70b8\u5371\u9669\u6027\uff0c\u4e00\u822c\u7684\u8bdd\uff0c\u6211\u4eec\u7528\u53e0\u6c2e\u78f7\u9178\u4e8c\u82ef\u916f(DPPA)\u6765\u4ee3\u66ff\u5176\u4f7f\u7528\u3002\u7528DPPA\u8fd8\u6709\u4e2a\u597d\u5904\u5c31\u662f\uff0c\u9178\u53ef\u4ee5\u76f4\u63a5\u5728\u6bd4\u8f83\u6e29\u548c\u7684\u6761\u4ef6\u4e0b\u5f62\u6210\u9170\u57fa\u53e0\u6c2e\u4e2d\u95f4\u4f53\uff0c\u7136\u540e\u8fdb\u884c\u5e93\u5c14\u63d0\u65af\u91cd\u6392\u53cd\u5e94\u3002<\/p>\n<p>&nbsp;<\/p>\n<ul>\n<li><strong>\u57fa\u672c\u6587\u732e<\/strong><\/li>\n<\/ul>\n<p>\u30fbCurtius, T. <em>Ber.<\/em> <strong>1890<\/strong>, <em>23<\/em>, 3023.<br \/>\n\u30fbCurtius, T. <em>J. Prakt. Chem.<\/em> <strong>1894<\/strong>, <em>50<\/em>,\u00a0275.<br \/>\n\u30fbShioiri, T.; Ninomiya, K.; Yamada, S.-i. <em>J. Am. Chem. Soc.<\/em>\u00a0<strong>1972<\/strong>, <em>94<\/em>, 6203. DOI: <a href=\"http:\/\/dx.doi.org\/10.1021\/ja00772a052\">10.1021\/ja00772a052<\/a><br \/>\n\u30fbNinomiya, K.; Shioiri, T.; Yamada, S.-i. <em>Tetrahedron<\/em> <strong>1974<\/strong>,\u00a0<em>30<\/em>, 2151. doi:<a href=\"http:\/\/dx.doi.org\/10.1016\/S0040-4020(01)97352-1\">10.1016\/S0040-4020(01)97352-1<\/a><br \/>\n\u30fbSmith, P. A. S. <em>Org. React.<\/em> <strong>1946<\/strong>, <em>3<\/em>,\u00a0337.<br \/>\n\u30fbScriven, E. F.; Turnbull, K.<em>Chem. Rev.<\/em> <strong>1988<\/strong>,\u00a0<em>88<\/em>, 297. DOI: <a href=\"http:\/\/dx.doi.org\/10.1021\/cr00084a001\">10.1021\/cr00084a001<\/a><br \/>\n\u30fbWolff, O.; Waldvogel, S. R.<em> Synthesis<\/em> <strong>2004<\/strong>,\u00a01303. DOI: <a href=\"http:\/\/dx.doi.org\/10.1055\/s-2004-815965\">10.1055\/s-2004-815965<\/a><\/p>\n<p>&nbsp;<\/p>\n<ul>\n<li><strong>\u53cd\u5e94\u673a\u7406<\/strong><\/li>\n<\/ul>\n<p>\u6c2e\u5bbe(nitrene)\u5f0f\u7684\u4e2d\u95f4\u4f53\u5f62\u6210\u540e\uff0c\u4fdd\u6301\u7acb\u4f53\u6784\u578b\u4e0d\u53d8\u8fdb\u884c\u91cd\u6392\u53cd\u5e94\u3002\u5f53R=H\u7684\u60c5\u51b5\u4e0b\uff0c\u540e\u7eed\u7684\u8131\u78b3\u9178\u5316\u53cd\u5e94\u540e\u5f62\u6210\u4e86\u80fa\u3002<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter\" src=\"http:\/\/www.chem-station.com\/odos\/images\/curtiu1.gif\" alt=\"curtiu1.gif\" width=\"532\" height=\"76\" \/><\/p>\n<p>&nbsp;<\/p>\n<ul>\n<li><strong>\u53cd\u5e94\u5b9e\u4f8b<\/strong><\/li>\n<\/ul>\n<p align=\"left\">DPPA\u53c2\u4e0e\u7684\u53cd\u5e94\u3002[1]\n<p align=\"left\"><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/03\/curtiu2.gif\"><img loading=\"lazy\" decoding=\"async\" class=\"size-full wp-image-657 aligncenter\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/03\/curtiu2.gif\" alt=\"curtiu2\" width=\"239\" height=\"94\" \/><\/a><\/p>\n<p align=\"left\">\u5bf9\u4e8e\u03b1-\u53d4\u80fa\u7b49\u5408\u6210\u6bd4\u8f83\u56f0\u96be\u7684\u7ed3\u6784\u8fd0\u7528\u6b64\u6761\u4ef6\u4e5f\u80fd\u591f\u5f88\u6709\u6548\u7684\u5408\u6210\u3002 [2]\n<p align=\"left\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter\" src=\"http:\/\/www.chem-station.com\/odos\/images\/curtius_4.gif\" alt=\"curtius_4.gif\" width=\"343\" height=\"105\" \/><\/p>\n<p align=\"left\">\u5965\u53f8\u4ed6\u97e6(Tamiflu)\u7684\u5408\u6210\u3002\u00a0[3]\n<ul>\n<li><strong>\u5b9e\u9a8c\u6b65\u9aa4<\/strong><\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n<ul>\n<li><strong>\u5b9e\u9a8c\u6280\u5de7<\/strong><\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n<ul>\n<li><strong>\u53c2\u8003\u6587\u732e<\/strong><\/li>\n<\/ul>\n[1] Zhang, Q. et al. <em>J. Org. Chem.<\/em> <strong>2000<\/strong>,\u00a0<em>65<\/em>, 7977. DOI: <a href=\"http:\/\/dx.doi.org\/10.1021\/jo000978e\">10.1021\/jo000978e<\/a><br \/>\n[2] Murashige, K. et al. <em>Tetrahedron<\/em> <strong>2002<\/strong>,\u00a0<em>58<\/em>, 4917. doi:<a href=\"http:\/\/dx.doi.org\/10.1016\/S0040-4020(02)00436-2\">10.1016\/S0040-4020(02)00436-2<\/a><br \/>\n[3] Yamatsugu, K.; Yin, L.; Kamijo, S.; Kimura, Y.; Kanai, M.; Shibasaki,\u00a0M. <em>Angew. Chem., Intl. Ed.<\/em> <strong>2009<\/strong>, <em>48,\u00a0<\/em>1070. DOI: <a href=\"http:\/\/dx.doi.org\/10.1002\/anie.200804777\">10.1002\/anie.200804777<\/a><\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp; <\/p>\n","protected":false},"excerpt":{"rendered":"&nbsp; \u6982\u8981 \u4ee5\u9178\u6216\u8005\u9170\u5364\u4f5c\u4e3a\u53cd\u5e94\u5e95\u7269\uff0c\u5f15\u53d1\u5f62\u6210\u7684\u9170\u57fa\u53e0\u6c2e\u4e2d\u95f4\u4f53\u5728\u52a0\u70ed\u6761\u4ef6\u4e0b\u91cd\u6392\uff0c\u5f62\u6210\u5f02\u6c30\u9178\u916f\u3002\u5982\u679c\u6b64\u65f6\uff0c\u6709\u6c34\u4ecb\u5165\u53cd\u5e94\u7684\u8bdd\uff0c\u5f02\u6c30\u9178\u916f\u4f1a\u7acb\u5373\u52a0\u6c34\u5206\u89e3\uff0c\u5f62\u6210\u8131\u6389\u4e00\u4e2a\u78b3\u7684\u80fa\u3002\u6b64\u5916\uff0c\u8be5\u65b9\u6cd5\u662f\u4e3a\u6570\u4e0d\u591a\u7684\u3001\u80fd\u591f\u5408\u6210\u5177\u6709\u5149\u5b66\u6d3b\u6027\u7684\u94fe\u72b6\u80fa\u7684\u65b9\u6cd5\u4e4b\u4e00\u3002 \u9664\u4e86\u6c34\u4ee5\u5916\uff0c\u5982\u679c\u4f7f\u7528\u4e00\u4e9b\u9002\u5f53\u7684\u9187\u4f5c\u4e3a\u53cd\u5e94\u5242\u7684\u8bdd\uff0c\uff0c\u5c31\u53ef\u4ee5\u5f88\u65b9\u4fbf\u7684\u5f62\u6210\u5404\u79cd\u6c28\u57fa\u9178\u916f\u7c7b\u57fa\u56e2\u4f5c\u4e3a\u80fa\u57fa\u7684\u4fdd\u62a4\u57fa\uff0c\u6bd4\u5982Boc\u3001Cbz\u7b49\u3002\u56e0\u6b64\uff0c\u6b64\u53cd\u5e94\u662f\u5e94\u7528\u6027\u6781\u5176\u9ad8\u7684\u4e00\u4e2a\u91cd\u6392\u53cd\u5e94\u3002 \u53e0\u6c2e\u94a0\u5177\u6709\u4e00\u5b9a\u7684\u7206\u70b8\u5371\u9669\u6027\uff0c\u4e00\u822c\u7684\u8bdd\uff0c\u6211\u4eec\u7528\u53e0\u6c2e\u78f7\u9178\u4e8c\u82ef\u916f(DPPA)\u6765\u4ee3\u66ff\u5176\u4f7f\u7528\u3002\u7528DPPA\u8fd8\u6709\u4e2a\u597d\u5904\u5c31\u662f\uff0c\u9178\u53ef\u4ee5\u76f4\u63a5\u5728\u6bd4\u8f83\u6e29\u548c\u7684\u6761\u4ef6\u4e0b\u5f62\u6210\u9170\u57fa\u53e0\u6c2e\u4e2d\u95f4\u4f53\uff0c\u7136\u540e\u8fdb\u884c\u5e93\u5c14\u63d0\u65af\u91cd\u6392\u53cd\u5e94\u3002 &nbsp; \u57fa\u672c\u6587\u732e \u30fbCurtius, T. Ber. 1890, 23, 3023. \u30fbCurtius, T. J. Prakt. Chem. 1894, 50,\u00a0275. \u30fbShioiri, T.; Ninomiya, K.; Yamada, S.-i. J. Am. Chem. Soc.\u00a01972, 94, 6203. DOI: 10.1021\/ja00772a052 \u30fbNinomiya, K.; Shioiri, T.; Yamada, S.-i. Tetrahedron 1974,\u00a030, 2151. doi:10.1016\/S0040-4020(01)97352-1 \u30fbSmith, P. A. S. Org. React. 1946, 3,\u00a0337. \u30fbScriven, E. F.; Turnbull, K.Chem. Rev. 1988,\u00a088, 297. DOI: 10.1021\/cr00084a001 \u30fbWolff, O.; Waldvogel, S. R. Synthesis 2004,\u00a01303. DOI: 10.1055\/s-2004-815965 &nbsp; \u53cd\u5e94\u673a\u7406 \u6c2e\u5bbe(nitrene)\u5f0f\u7684\u4e2d\u95f4\u4f53\u5f62\u6210\u540e\uff0c\u4fdd\u6301\u7acb\u4f53\u6784\u578b\u4e0d\u53d8\u8fdb\u884c\u91cd\u6392\u53cd\u5e94\u3002\u5f53R=H\u7684\u60c5\u51b5\u4e0b\uff0c\u540e\u7eed\u7684\u8131\u78b3\u9178\u5316\u53cd\u5e94\u540e\u5f62\u6210\u4e86\u80fa\u3002 &nbsp; \u53cd\u5e94\u5b9e\u4f8b DPPA\u53c2\u4e0e\u7684\u53cd\u5e94\u3002[1] \u5bf9\u4e8e\u03b1-\u53d4\u80fa\u7b49\u5408\u6210\u6bd4\u8f83\u56f0\u96be\u7684\u7ed3\u6784\u8fd0\u7528\u6b64\u6761\u4ef6\u4e5f\u80fd\u591f\u5f88\u6709\u6548\u7684\u5408\u6210\u3002 [2] \u5965\u53f8\u4ed6\u97e6(Tamiflu)\u7684\u5408\u6210\u3002\u00a0[3] \u5b9e\u9a8c\u6b65\u9aa4 &nbsp; \u5b9e\u9a8c\u6280\u5de7 &nbsp; \u53c2\u8003\u6587\u732e [1] Zhang, Q. et al. J. Org. Chem. 2000,\u00a065, 7977. DOI: 10.1021\/jo000978e [2] Murashige, K. et al. Tetrahedron 2002,\u00a058, 4917. doi:10.1016\/S0040-4020(02)00436-2 [3] Yamatsugu, K.; Yin, [&hellip;]","protected":false},"author":5,"featured_media":662,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"jetpack_post_was_ever_published":false,"_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":false,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_memberships_contains_paid_content":false,"footnotes":"","jetpack_publicize_message":"","jetpack_publicize_feature_enabled":true,"jetpack_social_post_already_shared":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","enabled":false},"version":2}},"categories":[2,12],"tags":[448,450,449],"jetpack_publicize_connections":[],"jetpack_featured_media_url":"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/03\/curtiu8.gif","jetpack_shortlink":"https:\/\/wp.me\/p96op1-aw","jetpack_sharing_enabled":true,"_links":{"self":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/652"}],"collection":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/users\/5"}],"replies":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/comments?post=652"}],"version-history":[{"count":2,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/652\/revisions"}],"predecessor-version":[{"id":28281,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/652\/revisions\/28281"}],"wp:featuredmedia":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media\/662"}],"wp:attachment":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media?parent=652"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/categories?post=652"},{"taxonomy":"post_tag","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/tags?post=652"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}