{"id":1407,"date":"2024-01-07T22:06:54","date_gmt":"2024-01-07T14:06:54","guid":{"rendered":"https:\/\/www.bdmaee.cn\/?p=1407"},"modified":"2024-01-07T22:31:05","modified_gmt":"2024-01-07T14:31:05","slug":"%e9%87%91%e5%b1%9e%e5%82%ac%e5%8c%96%e5%8f%8d%e5%ba%94%e5%b0%8f%e7%bb%93","status":"publish","type":"post","link":"https:\/\/www.bdmaee.cn\/archives\/1407","title":{"rendered":"\u91d1\u5c5e\u50ac\u5316\u53cd\u5e94\u5c0f\u7ed3"},"content":{"rendered":"

\u91d1\u5c5e\u50ac\u5316\u53cd\u5e94<\/strong><\/a>\u5c0f\u7ed3<\/p>\n

\u91d1\u5c5e\u50ac\u5316\u7684\u5076\u8054\u53cd\u5e94\u662f\u6709\u673a\u5408\u6210\u4e2d\u5e38\u89c1\u7684\u5f62\u6210\u78b3\u78b3\u952e\u7684\u53cd\u5e94\uff0c\u5728\u6709\u673a\u5408\u6210\u4e2d\u6709\u7740\u81f3\u5173\u91cd\u8981\u7684\u4f5c\u7528\u3002\u4e0b\u9762\u5bf9\u4e4b\u524d\u53d1\u8fc7\u7684\u6587\u7ae0\u8fdb\u884c\u6574\u7406\uff0c\u65b9\u4fbf\u5b66\u4e60\u3002\u70b9\u51fb\u53cd\u5e94\u7684\u6807\u9898\uff0c\u53ef\u4ee5\u67e5\u770b\u8be6\u7ec6\u5185\u5bb9\u3002<\/p>\n

\u91d1\u5c5e\u50ac\u5316\u7684\u53cd\u5e94\u4e2d\u94af\u50ac\u5316\u7684\u53cd\u5e94\u662f\u4e00\u7c7b\u7279\u522b\u6709\u7528\u7684\u53cd\u5e94\uff0c\u5b83\u63d0\u4f9b\u4e86\u4e00\u79cd\u5f62\u6210\u78b3-\u78b3\u952e\u7684\u72ec\u7279\u7684\u65b9\u6cd5\u3002\u8fd9\u7c7b\u53cd\u5e94\u7684\u4f18\u70b9\uff1a1\u3001\u4e0d\u9700\u8981\u52a0\u5165\u5176\u4ed6\u6c27\u5316\u5242\u50ac\u5316\uff1b2\u3001\u53ea\u9700\u50ac\u5316\u91cf\u7684\u94af\u50ac\u5316\u5242\u3002\u94af\u50ac\u5316\u7684\u63d2\u7fb0\u53cd\u5e94\u662f\u8fd9\u7c7b\u53cd\u5e94\u4e2d\u5e94\u7528\u4e3a\u5e7f\u6cdb\u7684\u53cd\u5e94\u4e4b\u4e00\uff0c\u5728\u8fd9\u91cc\u6211\u4eec\u5c06\u91cd\u70b9\u4ecb\u7ecd\u5b83\u3002<\/p>\n

\u4f17\u6240\u5468\u77e5\uff0c\u5728\u683c\u6c0f\u53cd\u5e94\u4e2d\u5355\u8d28\u9541\u91d1\u5c5e\u4e0e\u5e26\u6709sp3\u6742\u5316\u78b3\u539f\u5b50\u7684\u6709\u673a\u5364\u5316\u7269\uff08\u70f7\u57fa\u5364\u5316\u7269\uff09\u53cd\u5e94\u8981\u6bd4\u5e26\u6709sp2\u6742\u5316\u78b3\u539f\u5b50\u7684\u6709\u673a\u5364\u5316\u7269\uff08\u82b3\u57fa\u548c\u70ef\u57fa\u5364\u5316\u7269\uff09\u53cd\u5e94\u66f4\u5bb9\u6613\u3002\u800c\u4e0e\u6b64\u76f8\u53cd\uff0c\u94af\u7684\u7edc\u5408\u7269\u4e0e\u542b\u6709sp2\u6742\u5316\u78b3\u539f\u5b50\u7684\u6709\u673a\u5364\u5316\u7269\u53cd\u5e94\u66f4\u5bb9\u6613\u3002\u6362\u53e5\u8bdd\u8bf4\uff0c\u70ef\u57fa\u548c\u82b3\u57fa\u5364\u5316\u7269\u975e\u5e38\u5bb9\u6613\u4e0ePd(0)\u53d1\u751f\u6c27\u5316\u52a0\u6210\u53cd\u5e94\uff0c\u4ece\u800c\u751f\u6210\u542b\u6709\u94af-\u78b3\u0431-\u952e\u7684\u7edc\u5408\u7269\u4e2d\u95f4\u4f531\uff1b\u7136\u540e\uff0c\u4e0d\u9971\u548c\u5316\u5408\u7269\uff08\u4f8b\u5982\uff1a\u70ef\u70c3\u3001\u5171\u8f6d\u4e8c\u70ef\u3001\u7094\u70c3\u548c\u4e00\u6c27\u5316\u78b3\u7b49\uff09\u63d2\u5165\u5230\u94af-\u78b3\u952e\u4e4b\u95f4\uff1b\u540e\uff0c\u7ecf\u8fc7\u8fd8\u539f\u6d88\u53bb\u6216\u8005\u03b2-\u6c22\u6d88\u53bb\u53cd\u5e94\u751f\u6210\u76f8\u5e94\u7684\u76ee\u6807\u5316\u5408\u7269\u3002\u4e0e\u6b64\u540c\u65f6\uff0cPd(0)\u50ac\u5316\u5242\u5f97\u4ee5\u518d\u751f\u5e76\u5f00\u59cb\u65b0\u7684\u50ac\u5316\u5faa\u73af\u3002\u7531\u6b64\u53ef\u89c1\uff0c\u6b63\u662f\u56e0\u4e3a\u751f\u6210\u4e86\u8fd9\u79cd\u542b\u6709\u94af-\u78b3\u0431-\u952e\u7684\u7edc\u5408\u7269\u4e2d\u95f4\u4f53\uff0c\u624d\u4f7f\u5f97\u63a5\u4e0b\u6765\u7684\u63d2\u5165\u548c\u91d1\u5c5e\u8f6c\u79fb\u8fc7\u7a0b\u53d8\u6210\u53ef\u80fd\u3002<\/p>\n

\u5b9e\u9a8c\u8bc1\u660e\uff0cPd\u7684\u914d\u5408\u7269\u6bd4\u8f83\u5bb9\u6613\u4e0e\u7898\u5316\u7269\u548c\u6eb4\u5316\u7269\u53d1\u751f\u6c27\u5316\u52a0\u6210\u53cd\u5e94\u3002\u7898\u5316\u7269\u53ef\u4ee5\u5728\u4e0d\u52a0\u5165\u4efb\u4f55\u81a6\u914d\u4f53\u7684\u6761\u4ef6\u4e0b\uff0c\u53ea\u7528Pd(dba)3\u3001Pd(OAc)2\u751a\u81f3\u662fPd\/C\u4f5c\u50ac\u5316\u5242\u5373\u53ef\u53d1\u751f\u53cd\u5e94\u3002\u800c\u6eb4\u5316\u7269\u7684\u53cd\u5e94\u4e00\u822c\u662f\u9700\u8981\u81a6\u914d\u4f53\u7684\u3002\u4f46\u662f\u6c2f\u5316\u7269\u5728\u4e00\u822c\u7684\u6761\u4ef6\u4e0b\u662f\u975e\u5e38\u60f0\u6027\u7684\uff0c\u53ea\u6709\u7528\u8f83\u5f3a\u7ed9\u7535\u5b50\u6027\u7684\u5177\u6709\u53cc\u914d\u4f4d\u57fa\uff08bidentate\uff09\u7684\u914d\u4f53\uff08\u5982dppp\uff09\uff0c\u540c\u65f6\u5728\u975e\u5e38\u5267\u70c8\u7684\u6761\u4ef6\u4e0b\u624d\u80fd\u53d1\u751f\u53cd\u5e94\u3002\u4f8b\u5982\u6c2f\u82ef\u7684\u94af\u50ac\u5316\u53cd\u5e94\u5f80\u5f80\u8981\u52a0\u5165Cr(CO)3\uff0c\u76ee\u7684\u662f\u5229\u7528\u5b83\u7684\u5f3a\u5438\u7535\u5b50\u6027\u6d3b\u5316Cl-C\u952e\u3002\u5e94\u8be5\u6307\u51fa\u7684\u662f\uff0c\u4e3a\u4e86\u4e2d\u548c\u53cd\u5e94\u751f\u6210\u7684HX\u9178\uff0c\u78b1\uff08R3N\u3001NaOAc\u3001KOAc\u3001Na2CO3\u3001K2CO3\u7b49\uff09\u7684\u4f7f\u7528\u662f\u5fc5\u9700\u7684\u3002<\/p>\n

\"\"<\/p>\n

\u9664\u4e86\u5364\u5316\u7269\u4ee5\u5916\uff0c\u7c7b\u5364\u5316\u7269R-X = ArCO-Cl, ArSO2-Cl,Ar-N2+X-, R-OP(O)(OR)2, R-OSO2CF3(OTf), R-OSO2Rf (Rf = perfluoroaikyl), R-OSO2F,R-OSO2CH3\u548cAr-ArI+\u662f\u5f88\u597d\u7684\u79bb\u53bb\u57fa\u56e2\uff0c\u5b83\u4eec\u4e5f\u80fd\u4e0ePd(0)\u53d1\u751f\u6c27\u5316\u52a0\u6210\u53cd\u5e94\u4ece\u800c\u5f62\u6210\u82b3\u57fa\u548c\u70ef\u57fa\u94af\u914d\u5408\u7269\u4e2d\u95f4\u4f53\u3002\u4f46\u662f\uff0c\u8fd9\u4e9b\u79bb\u53bb\u57fa\u56e2\u5bf9\u4e8ePd(0)\u7684\u53cd\u5e94\u6d3b\u6027\u662f\u5404\u4e0d\u76f8\u540c\u7684\uff0c\u5b83\u4eec\u4e2d\u7684\u67d0\u4e9b\u5316\u5408\u7269\u5f80\u5f80\u53ea\u80fd\u548c\u67d0\u4e9b\u7279\u5b9a\u7684\u5e95\u7269\u5728\u975e\u5e38\u7279\u6b8a\u6761\u4ef6\u4e0b\u53d1\u751f\u53cd\u5e94\u3002<\/p>\n

\u6709\u7528\u7684\u7c7b\u5364\u5316\u7269\u662f\u915a\u7684\u4e09\u6c1f\u7532\u78fa\u9178\u82b3\u57fa\u916f\u548c\u4ece\u7fb0\u57fa\u5316\u5408\u7269\u6d3e\u751f\u51fa\u6765\u7684\u4e09\u6c1f\u7532\u78fa\u9178\u70ef\u9187\u916f\u3002\u82b3\u9170\u57fa\u5364\u5316\u7269\u548c\u78fa\u9170\u57fa\u5364\u5316\u7269\u901a\u8fc7\u5148\u4e0ePd(0)\u53d1\u751f\u6c27\u5316\u52a0\u6210\u53cd\u5e94\uff0c\u7d27\u63a5\u7740\u8131\u53bbCO\u548cSO2\u5c31\u5f62\u6210\u4e86\u82b3\u57fa\u94af\u914d\u5408\u7269\u3002\u53e6\u5916\uff0c\u82ef\u7684\u91cd\u6c2e\u76d0\u662f\u5f62\u6210\u82b3\u57fa\u94af\u914d\u5408\u7269\u7684\u6d3b\u6cfc\u53cd\u5e94\u6e90\u3002<\/p>\n

\u70f7\u57fa\u5364\u5316\u7269\u548cPd(0)\u7684\u6c27\u5316\u52a0\u6210\u53cd\u5e94\u662f\u975e\u5e38\u7f13\u6162\u7684\u3002\u800c\u4e14\uff0c\u901a\u8fc7\u70f7\u57fa\u5364\u5316\u7269\u7684\u6c27\u5316\u52a0\u6210\u53cd\u5e94\u5f97\u5230\u7684\u70f7\u57fa\u94af\u914d\u5408\u7269\u7ecf\u8fc7\u03b2-\u6c22\u6d88\u9664\u4e4b\u540e\uff0c\u53cd\u5e94\u5c31\u505c\u6b62\u5728\u8fd9\u4e00\u9636\u6bb5\uff0c\u800c\u4e0d\u518d\u8fdb\u884c\u63d2\u5165\u6216\u91d1\u5c5e\u8f6c\u79fb\u8fc7\u7a0b\u3002\u5bf9\u4e8e\u7094\u57fa\u5364\u5316\u7269\u6765\u8bf4\uff0c\u867d\u7136\u6ca1\u6709\u592a\u591a\u7684\u6587\u732e\u62a5\u9053\uff0c\u4f46\u662f\u7094\u57fa\u7898\u5316\u7269\u7684\u786e\u53ef\u4ee5\u548cPd(0)\u53cd\u5e94\u751f\u6210\u7094\u57fa\u94af\u914d\u5408\u7269\u3002<\/p>\n

\u53e6\u5916\u8fd8\u6709\u954d\u50ac\u5316\u548c\u94dc\u50ac\u5316\u7684\u53cd\u5e94\u4e5f\u6709\u51e0\u4e2a\u7ecf\u5178\u53cd\u5e94\uff0c\u4e0b\u9762\u90fd\u6709\u4ecb\u7ecd\u3002<\/p>\n

\u4e00\u3001Buchwald_Hartwig\u53cd\u5e94\uff0c\u5e03\u8d6b\u74e6\u5c14\u5fb7-\u54c8\u7279\u7ef4\u5e0c\u5076\u8054\u53cd\u5e94(Buchwald-Hartwig cross coupling)<\/p>\n

Buchwald\u2013Hartwig\u82b3\u80fa\u5316\u53cd\u5e94\u662f\u975e\u5e38\u5e38\u7528\u7684\u7531\u82b3\u57fa\u5364\u4ee3\u7269\u6216\u82b3\u57fa\u78fa\u9178\u916f\u5236\u5907\u82b3\u80fa\u7684\u53cd\u5e94\u3002\u6b64\u53cd\u5e94\u7684\u4e3b\u8981\u7279\u70b9\u662f\u5229\u7528\u50ac\u5316\u91cf\u7684\u94af\u548c\u5bcc\u7535\u5b50\u914d\u4f53\u8fdb\u884c\u50ac\u5316\u53cd\u5e94\u3002\u53e6\u5916\u5f3a\u78b1\uff08\u5982\u53d4\u4e01\u9187\u94a0\uff09\u5bf9\u4e8e\u50ac\u5316\u5faa\u73af\u662f\u81f3\u5173\u91cd\u8981\u7684\u3002<\/p>\n

\u4e8c\u3001Cadiot-Chodkiewicz\u5076\u8054\u53cd\u5e94<\/p>\n

\u4e00\u4ef7\u94dc\u4f5c\u4e3a\u50ac\u5316\u5242\uff0c\u7aef\u57fa\u7094\u548c\u7094\u57fa\u5364\u5316\u7269\u53cd\u5e94\u751f\u6210\u975e\u5bf9\u79f0\u6027\u4e8c\u7094\u7684\u53cd\u5e94<\/p>\n

\u4e09\u3001\u7fb0\u57fa\u5316\u5076\u8054\u53cd\u5e94 Carbonylative Cross Coupling<\/p>\n

\u5229\u7528\u4e00\u6c27\u5316\u78b3\u80fd\u63d2\u5165\u78b3-\u91d1\u5c5e\u952e\u8fd9\u4e00\u7279\u6027\uff0c\u5728\u5076\u8054\u53cd\u5e94\u4e2d\u540c\u65f6\u5f15\u5165\u7fb0\u57fa\uff0c\u751f\u6210\u916f\uff0c\u9170\u80fa\uff0c\u916e\uff0c\u9187\u7b49\u4ea7\u7269\u3002\u5728\u6709\u673a\u5408\u6210\u4e2d\u662f\u4e00\u4e2a\u975e\u5e38\u6709\u6548\u7387\u7684\u53cd\u5e94\u3002\u5e38\u7528\u4e8e\u94af\u50ac\u5316\u5076\u8054\u53cd\u5e94\u3002<\/p>\n

\u6211\u4eec\u77e5\u9053\u4e00\u6c27\u5316\u78b3\u5f88\u5bb9\u6613\u63d2\u5165\u78b3-\u91d1\u5c5e\u952e\u4e4b\u95f4\u3002\u7528\u94af\u50ac\u5316\u5242\uff0c\u6709\u57fa\u5364\u5316\u7269\uff0c\u4e00\u6c27\u5316\u78b3\uff0c\u9187\u4e00\u8d77\u53cd\u5e94\u4f1a\u751f\u6210\u916f\u3002\u7528\u80fa\u4ee3\u66ff\u5176\u4e2d\u7684\u9187\u4f1a\u5f97\u5230\u9170\u80fa\uff0c\u7528\u6c22\u6e90\u66ff\u4ee3\u9187\u4f1a\u5f97\u5230\u919b\uff0c\u6362\u6210\u6709\u673a\u91d1\u5c5e\u8bd5\u5242\u5c31\u4f1a\u5f97\u5230\u916e\u3002<\/p>\n

\u56db\u3001Castro\u2013Stephens\u5076\u8054\u53cd\u5e94(Castro-Stephens Coupling)<\/p>\n

\u7094\u5316\u4e9a\u94dc\u4e0e\u82b3\u5364\u53d1\u751f\u4ea4\u53c9\u5076\u8054\uff0c\u751f\u6210\u4e8c\u53d6\u4ee3\u7094\u53ca\u5364\u5316\u4e9a\u94dc\u3002 \u8fd9\u4e2a\u53cd\u5e94\u7531 C. E. Castro \u548c R. D. Stephens \u5728 1963 \u5e74\u53d1\u73b0\u3002\u73b0\u5728\u88ab\u5927\u5bb6\u6240\u719f\u77e5\u7684\u662f\u5176\u6539\u826f\u6cd5Sonogashira\u5076\u8054.<\/p>\n

\u4e94\u3001Chan\u2013Lam C\u2013X\u5076\u8054\u53cd\u5e94\uff0cChan-Lam-Evans\u5076\u8054\u53cd\u5e94(Chan-Lam-Evans Coupling)<\/p>\n

\u542b\u6709NH\/OH\/SH\u57fa\u56e2\u7684\u5e95\u7269\u5728\u5f31\u78b1\u6761\u4ef6\u4e0b\uff0c\u5728\u7a7a\u6c14\u4e2d\u901a\u8fc7\u918b\u9178\u94dc\u50ac\u5316\uff0c\u4e0e\u6709\u673a\u787c\u9178\u5316\u5408\u7269\u6c27\u5316\u4ea4\u53c9\u5076\u8054\u8fdb\u884c\u82b3\u57fa\uff0c\u70ef\u57fa\u548c\u70f7\u57fa\u5316\u7684\u53cd\u5e94\u3002<\/p>\n

\u516d\u3001\u4ea4\u53c9\u8131\u6c22\u5076\u8054\u53cd\u5e94(Cross Dehydrogenative Coupling (CDC))<\/p>\n

\u5728\u4e24\u4e2a\u5e95\u7269\u7684C-H\u88ab\u6d3b\u5316\u7684\u60c5\u51b5\u4e0b\uff0c\u5229\u7528\u6c22acceptor(\u6c27\u5316\u5242)\u7684\u4f5c\u7528\uff0c\u8fdb\u884c\u7684\u4ea4\u53c9\u578bC-C\u5076\u8054\u53cd\u5e94\u3002\u5982\u679c\u6c27\u5316\u5242\u662f\u5206\u5b50\u72b6\u7684\u6c27\u6c14\u7684\u8bdd\uff0c\u7406\u8bba\u4e0a\u751f\u6210\u7684\u526f\u4ea7\u7269\u5c31\u662f\u6c34\u800c\u5df2\uff0c\u8fd9\u6837\u8fd9\u6837\u7684\u53cd\u5e94\u5c31\u662f\u975e\u5e38\u4f18\u79c0\u7684\u7eff\u8272\u5316\u5b66\u3002\u56e0\u6b64\uff0c\u4e00\u65e6\u5b9e\u73b0\u7684\u8bdd\u8fd9\u4e2a\u53cd\u5e94\u4e5f\u88ab\u8ba4\u4e3a\u662f\u7ec8\u6781\u7684\uff0c\u7406\u60f3\u7684\u53cd\u5e94\u5f62\u5f0f\u3002<\/p>\n

\u4e03\u3001Eglinton\u5076\u8054<\/p>\n

\u7aef\u57fa\u7094\u5728\u5316\u5b66\u8ba1\u91cf\uff08\u6216\u8fc7\u91cf\uff09\u7684Cu(OAc)2\u7684\u50ac\u5316\u4e0b\u8fdb\u884c\u6c27\u5316\u5076\u8054\u7684\u53cd\u5e94\u3002\u6b64\u53cd\u5e94\u662fGlaser \u5076\u8054\u53cd\u5e94\u7684\u4e00\u4e2a\u53d8\u4f53\u3002<\/p>\n

\u516b\u3001Eschenmoser\u5076\u8054(Eschenmoser Coupling)<\/p>\n

\u786b\u4ee3\u9170\u80fa\u901a\u8fc7\u70f7\u57fa\u5316\u751f\u6210vinylogous amides\u6216\u8005\u805a\u6c28\u916f\u7684\u624b\u6cd5\u3002<\/p>\n

\u4e5d\u3001Fukuyama\u5076\u8054\u53cd\u5e94<\/p>\n

\u6709\u673a\u950c\u5316\u5408\u7269\u548c\u786b\u4ee3\u9178\u916f\u5728\u94af\u50ac\u5316\u5242\u4e0b\u5076\u8054\u5f97\u5230\u916e\u7684\u53cd\u5e94\u3002\u6b64\u53cd\u5e94\u662fTohru Fukuyama\u57281998\u5e74\u53d1\u73b0\u3010Tetrahedron Letters. 39 (20): 3189\u20133192\u3011\uff0c\u662f\u65b0\u53d1\u73b0\u7684\u7ecf\u5178\u94af\u50ac\u5316\u5076\u8054\u53cd\u5e94\u3002\u6b64\u53cd\u5e94\u5316\u5b66\u9009\u62e9\u6027\u9ad8\uff0c\u53cd\u5e94\u6761\u4ef6\u6e29\u548c\uff0c\u6240\u7528\u8bd5\u5242\u4f4e\u6bd2\u3002\u7531\u4e8e\u6709\u673a\u950c\u8bd5\u5242\u53cd\u5e94\u6d3b\u6027\u8f83\u4f4e\uff0c\u6240\u4ee5\u6b64\u53cd\u5e94\u6709\u5f88\u597d\u7684\u5b98\u80fd\u56e2\u8010\u53d7\u5ea6\uff0c\u916e\uff0c\u916f\uff0c\u786b\u919a\uff0c\u82b3\u57fa\u6eb4\uff0c\u82b3\u57fa\u6c2f\u548c\u919b\u7b49\u6b64\u53cd\u5e94\u6761\u4ef6\u4e0b\u90fd\u53ef\u4ee5\u7a33\u5b9a\u5b58\u5728\u3002<\/p>\n

Fujiwara-Moritani Reaction(\u85e4\u539f-\u5b88\u8c37\u53cd\u5e94)<\/p>\n

Pd\u50ac\u5316\u5242\u5b58\u5728\u4e0b\uff0c\u5bf9\u65e0\u4fee\u9970\u7684\u82ef\u73af\u8fdb\u884c\u7684\u76f4\u63a5\u7684\u70ef\u70c3\u5316\u5076\u8054\u53cd\u5e94\u3002\u4e5f\u662f\u50ac\u5316C-H\u6d3b\u5316\u7684\u4e00\u4e2a\u4f8b\u5b50\u3002\u53cd\u5e94\u5f62\u5f0f\u57fa\u672c\u4e0eHeck\u53cd\u5e94\u76f8\u5f53\u3002<\/p>\n

\"\"<\/p>\n

\u5341\u3001Goldberg\u5076\u8054\u53cd\u5e94<\/p>\n

\u94dc\u6216\u94dc\u76d0\u50ac\u5316\u4e0b\u8fdb\u884c\u82b3\u9170\u80fa\u5316\u7684\u53cd\u5e94\u3002\u6b64\u53cd\u5e94\u65e9\u7531\u5fb7\u56fd\u5973\u5316\u5b66\u5bb6\u3001Fritz Ullmann \u7684\u59bb\u5b50 Irma Goldberg \u53d1\u73b0\u3002\u4f46\u6b64\u53cd\u5e94\u6709\u4e00\u4e9b\u7f3a\u70b9\uff1a\uff081\uff09\u53cd\u5e94\u6e29\u5ea6\u4e00\u822c\u662f140\u2103\uff0c\u751a\u81f3\u66f4\u9ad8\uff1b\uff082\uff09\u90e8\u5206\u7684\u53cd\u5e94\u9700\u8981\u4e00\u4e2a\u6469\u5c14\u6216\u66f4\u591a\u7684\u94dc\u53c2\u4e0e\u53cd\u5e94\uff1b\uff083\uff09\u4e00\u822c\u9700\u8981\u5728\u9ad8\u6781\u6027\u800c\u4e14\u6bd2\u6027\u8f83\u5927\u7684\u6eb6\u5242\u4e2d\u8fdb\u884c\u3002\u8fd1\u5e74\u6765\uff0c\u5229\u7528\u5408\u9002\u7684\u914d\u4f53\uff0c\u628a\u94dc\u7684\u4f7f\u7528\u91cf\u7f29\u51cf\u5230\u4e86\u50ac\u5316\u91cf\u3002\u8be5\u53cd\u5e94\u4e0d\u9700\u8981\u4f7f\u7528\u6602\u8d35\u7684Pd\u91d1\u5c5e\uff0c\u5728\u7ecf\u6d4e\u6027\u4e0a\u662f\u5341\u5206\u6709\u4f18\u52bf\u7684\u3002<\/p>\n

\u5341\u4e00\u3001\u683c\u62c9\u6cfd\u5076\u8054\u53cd\u5e94(Glaser Reaction)<\/p>\n

\u683c\u62c9\u6cfd\u5076\u8054\u53cd\u5e94\uff08Glaser coupling\uff09\uff0c\u4ee5\u7814\u7a76\u8005\u5361\u5c14\u00b7\u683c\u62c9\u6cfd\u7684\u540d\u5b57\u547d\u540d\u3002\u4e24\u5206\u5b50\u672b\u7094\u5728\u78b1\u548c\u94dc\u76d0\u4f5c\u7528\u4e0b\uff0c\u5076\u8054\u4e3a\u53cc\u7094\u3002\u6b64\u53cd\u5e94\u662f\u53e4\u8001\u7684\u7094\u5076\u8054\u53cd\u5e94\u3002\u4e00\u4ef7\u94dc\u76d0\u4e3a\u53cd\u5e94\u6240\u5fc5\u9700\uff0c\u5e38\u89c1\u7684\u662f\u6c2f\u5316\u4e9a\u94dc\u3001\u6eb4\u5316\u4e9a\u94dc\u548c\u4e59\u9178\u4e9a\u94dc\u3002\u6c28\u662f\u7ecf\u5178\u7684\u6240\u7528\u78b1\uff0c\u7528\u4e8e\u593a\u53d6\u7094\u7684\u9178\u6027CH\u8d28\u5b50\u3002\u6eb6\u5242\u53ef\u4ee5\u662f\u6c34\u6216\u4e59\u9187\u3002\u53cd\u5e94\u7ecf\u53cc\u6838\u7684\u3001\u542b\u6865\u8fde\u7684\u7094\u914d\u4f53\u7684\u94dc\u7edc\u5408\u7269\u4e2d\u95f4\u4f53\u3002\u6c27\u6c14\u7528\u4e8e\u94dc\u50ac\u5316\u5242\u7684\u91cd\u65b0\u6c27\u5316\u3002<\/p>\n

\u5341\u4e8c\u3001Heck \u53cd\u5e94\uff0cHeck\u53cd\u5e94<\/p>\n

\u94af\u50ac\u5316\u4e0b\u5bf9\u70ef\u70c3\u8fdb\u884c\u70ef\u57fa\u6216\u82b3\u57fa\u5316\u7684\u53cd\u5e94\u3002\u53e6\u5916\u4e0d\u542b\u03b2\u6c22\u7684\u5364\u4ee3\u70c3\uff08\u4e3b\u8981\u662f\u5364\u5316\u82c4\uff09\u4e5f\u53ef\u53d1\u751fHeck\u53cd\u5e94\uff0c\u8fdb\u884c\u70f7\u57fa\u5316\u3002<\/p>\n

\u5341\u4e09\u3001\u82b3\u9999\u6742\u73afHeck\u53cd\u5e94<\/p>\n

\u82b3\u9999\u6742\u73af\u4f5c\u4e3a\u53d7\u4f53\u7684\u53d1\u751f\u5728\u5206\u5b50\u5185\u6216\u5206\u5b50\u95f4\u7684Heck\u53cd\u5e94\u3002<\/p>\n

\u5341\u56db\u3001\u91cd\u6c2e\u76d0\u53c2\u4e0e\u7684Heck \u53cd\u5e94\u56fe\u7247<\/p>\n

\u82b3\u57fa\u91cd\u6c2e\u76d0\u53ef\u4ee5\u53d1\u751f\u7684\u53cd\u5e94\u5e38\u89c1\u7684\u5c31\u662fSandmeyer\u53cd\u5e94\u53ef\u4ee5\u5236\u5907\u5364\u4ee3\u82b3\u70c3\uff0c\u82b3\u57fa\u915a\u6216\u82b3\u57fa\u8148\uff0c\u53e6\u5916\u5c31\u662fBalz-Schiemann\u53cd\u5e94\u5236\u5907\u82b3\u57fa\u6c1f\u5316\u7269\uff0c\u5076\u6c2e\u5076\u5408\u53cd\u5e94\u5236\u5907\u5076\u6c2e\u4e8c\u82b3\u57fa\u7c7b\u5316\u5408\u7269\u30021995\u5e74Beller\u7b49\u4eba\u62a5\u9053\u4e86\u5229\u7528\u91cd\u6c2e\u76d0\u4f5c\u4e3a\u5e95\u7269\u8fdb\u884cHeck\u53cd\u5e94\u5236\u5907\u82b3\u57fa\u70ef\u57fa\u5316\u7269\uff0c\u8fd9\u662f\u4e00\u79cd\u5f88\u5b9e\u7528\u7684\u5236\u5907\u82b3\u57fa\u70ef\u70c3\u7684\u53cd\u5e94\uff0c\u6b64\u7c7b\u53cd\u5e94\u4e0d\u9700\u8981\u81a6\u50ac\u5316\u5242\u548c\u80fa\uff0c\u6761\u4ef6\u6e29\u548c\u3002<\/p>\n

\u5341\u4e94\u3001\u94af\u50ac\u5316\u7684Hiyama\u5076\u8054\u53cd\u5e94\u793a\u4f8b\uff0c\u6867\u5c71\u5076\u8054\u53cd\u5e94\uff08Hiyama Cross Coupling\uff09<\/p>\n

\u94af\u50ac\u5316\u4e0b\u6709\u673a\u7845\u8bd5\u5242\u548c\u6709\u673a\u5364\u4ee3\u7269\u6216\u4e09\u6c1f\u7532\u78fa\u9178\u916f\u8fdb\u884c\u4ea4\u53c9\u5076\u8054\u7684\u53cd\u5e94\u3002\u53cd\u5e94\u4e2d\u5e38\u5e38\u52a0\u5165\u4e00\u79cd\u6c1f\u5316\u7269\uff08TASF\u3001TBAF\uff09\u6216\u78b1\uff08\u5982\u6c22\u6c27\u5316\u94a0\u3001\u78b3\u9178\u94a0\uff09\u7684\u6d3b\u5316\u8bd5\u5242\uff0c\u5426\u5219\u53cd\u5e94\u4f1a\u5f88\u96be\u8fdb\u884c\u3002\u50ac\u5316\u5faa\u73af\u548cKumada\u5076\u8054\u7c7b\u4f3c\u3002<\/p>\n

\u7845\u4e0a\u7684\u53d6\u4ee3\u57fa\u901a\u5e38\u5fc5\u987b\u662f\u6742\u539f\u5b50\u6216\u8005\u82ef\u57fa\u3002\u5982\u679c\u662f\u4e09\u70f7\u57fa\u7532\u7845\u70f7\uff0c\u5219\u96be\u4ee5\u5f62\u6210\u7845\u9178\u76d0\u4e2d\u95f4\u4f53\uff0c\u6240\u4ee5\u5076\u8054\u53cd\u5e94\u8f83\u96be\u8fdb\u884c\u3002\u7845\u5177\u6709\u4f4e\u6bd2\u6027\u7684\u4f18\u70b9\uff0c\u662f\u4e00\u4e2a\u5f88\u6709\u6f5c\u529b\u7684\u53cd\u5e94\u3002<\/p>\n

\u5341\u516d\u3001Kagan-Molander\u5076\u8054\u53cd\u5e94<\/p>\n

\u4e0a\u4e16\u7eaa70\u5e74\u4ee3\u672b\uff0cH. Kagan\u7cfb\u7edf\u5730\u7684\u7814\u7a76\u4e86\u4e8c\u4ef7\u9567\u7cfb\u91d1\u5c5e\u7898\u5316\u7269\u7684\u8fd8\u539f\u7279\u6027\uff0c\u5e76\u5728\u8fd9\u4e00\u7814\u7a76\u7684\u57fa\u7840\u4e0a\uff0c\u53d1\u73b0\u5728\u4e24\u500d\u5f53\u91cf\u7684\u4e8c\u7898\u5316\u9490\u5b58\u5728\u4e0b\u6eb4\u4ee3\u70f7\uff0c\u7898\u4ee3\u70f7\u6216TsO\u70f7\u4e0e\u919b\u916e\u53cd\u5e94\u53ef\u4ee5\u751f\u6210\u76f8\u5e94\u7684\u9187\u3002\u521d\u7684\u53cd\u5e94\u6761\u4ef6\u662f\u4ee5\u56db\u6c22\u544b\u5583\u4e3a\u6eb6\u5242\u5ba4\u6e29\u4e0b\u53cd\u5e9424\u5c0f\u65f6\u6216\u56de\u6d41\u51e0\u5c0f\u65f6\u3002Kagan\u4e5f\u53d1\u73b0\u5728\u53cd\u5e94\u4e2d\u52a0\u5165\u50ac\u5316\u91cf\u7684\u6c2f\u5316\u94c1\u53ef\u4ee5\u660e\u663e\u5730\u51cf\u5c11\u53cd\u5e94\u65f6\u95f4\uff0c\u800c\u8fd9\u4e00\u65b9\u6cd5\u5728\u540e\u6765\u88abG.A. Molander\u8fdb\u4e00\u6b65\u7684\u7814\u7a76\u53d1\u5c55\u3002\u57281984\u5e74G.A.Molander\u6b21\u62a5\u9053\u4e86\u5728\u5206\u5b50\u5185\u53d1\u751f\u7684\u6b64\u53cd\u5e94\uff0c\u03c9-\u7898\u4ee3\u916f\u5728\u4e8c\u7898\u5316\u9490\u548c\u50ac\u5316\u91cf\u7684\u4e09\u4ef7\u94c1\u76d0\u7684\u5b58\u5728\u4e0b\u53d1\u751f\u5206\u5b50\u5185\u7684\u9170\u57fa\u53d6\u4ee3\u53cd\u5e94\uff0c\u5e76\u8fdb\u4e00\u6b65\u53d1\u751f\u6b64\u53cd\u5e94\u751f\u6210\u590d\u5408\u591a\u73af\u8102\u70c3\u3002\u73b0\u5728\u6b64\u7c7b\u53cd\u5e94\u88ab\u7edf\u79f0\u4e3aKagan-Molander\u4e8c\u7898\u5316\u9490\u4ecb\u5bfc\u5076\u8054\u3002<\/p>\n

\"\"<\/p>\n

\u5341\u4e03\u3001Kochi-F\u00fcrstner\u5076\u8054\u53cd\u5e94(Kochi-F\u00fcrstner Cross Coupling)<\/p>\n

\u5364\u5316\u82b3\u70c3\u30fb\u82b3\u57fa\u4e09\u6c1f\u7532\u78fa\u9178\u30fb\u82b3\u57fa\u78fa\u9178\u76d0\u4e0eGrignard\u8bd5\u5242\u5728\u94c1\u50ac\u5316\u5242\u7684\u4f5c\u7528\u4e0b\u8fdb\u884c\u7684\u5076\u8054\u53cd\u5e94\u3002\u6c2f\u5316\u82b3\u70c3\u662f\u8be5\u53cd\u5e94\u597d\u7684\u5e95\u7269\u3002\u800c\u6eb4\u5316\u82b3\u70c3\u4e0e\u7898\u5316\u82b3\u70c3\u5728\u8be5\u6761\u4ef6\u4e0b\u4f18\u5148\u53d1\u751f\u8131\u5364\u7d20\u5316\u53cd\u5e94\u3002<\/p>\n

\u5341\u516b\u3001Kumada\u5076\u8054\u53cd\u5e94<\/p>\n

Kumada\u5076\u8054\u53cd\u5e94\u662f1972\u5e74\u9996\u5148\u53d1\u73b0\u7684Pd \u6216 Ni\u50ac\u5316\u7684\u5076\u8054\u53cd\u5e94\uff0c\u6b64\u53cd\u5e94\u662f\u683c\u6c0f\u8bd5\u5242\u548c\u70f7\u57fa\uff0c\u70ef\u57fa\u6216\u82b3\u57fa\u5364\u4ee3\u7269\u5076\u8054\u7684\u5f88\u7ecf\u6d4e\u7684\u53cd\u5e94\uff0c\u7f3a\u70b9\u662f\u5e76\u4e0d\u662f\u6240\u6709\u7684\u5364\u4ee3\u7269\u90fd\u80fd\u4e0e\u6709\u673a\u9541\u5316\u5408\u7269\u8fdb\u884c\u53cd\u5e94\u3002Kumada\u5076\u8054\u5728\u5de5\u4e1a\u4e0a\u7684\u4e00\u4e2a\u91cd\u8981\u5e94\u7528\u662f\u5408\u6210\u82ef\u4e59\u70ef\u7c7b\u884d\u751f\u7269\uff0c\u662f\u4f4e\u6210\u672c\u5408\u6210\u4e0d\u5bf9\u79f0\u7684\u8054\u82b3\u57fa\u5316\u5408\u7269\u7684\u53cd\u5e94\u3002<\/p>\n

\u672c\u53cd\u5e94\u4e0eNegishi Coupling\u4e0d\u540c\uff0c\u53ef\u4ee5\u76f4\u63a5\u548c\u683c\u6c0f\u8bd5\u5242\u53cd\u5e94\uff0c\u800c\u4e0d\u9700\u8981\u5148\u8f6c\u5316\u4e3a\u6709\u673a\u950c\u8bd5\u5242\u3002<\/p>\n

Kumada\uff08\u4ea4\u53c9\uff09\u5076\u8054\u53cd\u5e94\uff08\u718a\u7530\u5076\u8054\uff1bKumadacoupling\uff09\uff0c\u53c8\u79f0Kumada-Corriu\uff08\u4ea4\u53c9\uff09\u5076\u8054\u53cd\u5e94\uff0c\u718a\u7530-\u7389\u5c3e-Corriu\u5076\u8054\u53cd\u5e94(Kumada-Tamao-Corriu Cross Coupling)\u3002\u662f\u6307\u70f7\u57fa\u6216\u82b3\u57fa\u683c\u6c0f\u8bd5\u5242\u4e0e\u82b3\u5364\u6216\u4e59\u70ef\u57fa\u5364\uff0c\u82b3\u57fa\u4e09\u6c1f\u7532\u78fa\u9178\u916f\u7b49\u7b49\u5728\u954d\u6216\u94af\u50ac\u5316\u4e0b\u7684\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\u3002<\/p>\n

\u5341\u4e5d\u3001McMurry\u5076\u8054\u53cd\u5e94<\/p>\n

\u4f4e\u4ef7\u949b[\u5982TiCl3\/LiAlH4\u751f\u6210\u7684Ti(0)]\u50ac\u5316\u7fb0\u57fa\u5236\u5907\u70ef\u70c3\u7684\u53cd\u5e94\u3002\u6b64\u53cd\u5e94\u662f\u5355\u7535\u5b50\u8f6c\u79fb\u5386\u7a0b\u3002<\/p>\n

\u4e8c\u5341\u3001Negishi\u4ea4\u53c9\u5076\u8054\u53cd\u5e94<\/p>\n

\u5728\u954d\u6216\u94af\u50ac\u5316\u4e0b\u6709\u673a\u950c\u8bd5\u5242\u548c\u5404\u79cd\u5364\u4ee3\u7269\u6216\u78fa\u9178\u916f\uff08\u82b3\u57fa\uff0c\u70ef\u57fa\uff0c\u7094\u57fa\u548c\u9170\u57fa\uff09\u8fdb\u884c\u4ea4\u53c9\u5076\u8054\u7684\u53cd\u5e94\u3002<\/p>\n

\u53cd\u5e94\u6d3b\u6027\u4e00\u822c\u6bd4\u8f83\u597d\u3001\u5bf9\u70f7\u57fa(sp3) \u950c\u5316\u5408\u7269\u4e5f\u80fd\u4f7f\u7528\uff0c\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u597d\u3002<\/p>\n

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