{"id":40274,"date":"2021-10-08T08:00:19","date_gmt":"2021-10-08T00:00:19","guid":{"rendered":"\/\/www.gsbet888.com\/?p=40274"},"modified":"2021-10-06T12:21:05","modified_gmt":"2021-10-06T04:21:05","slug":"org-lett-%ef%bc%9a%e8%8a%b3%e5%9f%ba%e7%a2%98%e4%b8%8e%e8%8b%af%e5%b9%b6%e5%91%8b%e5%96%83%e4%b9%8b%e9%97%b4%e7%9a%84c-h%e8%8a%b3%e5%9f%ba%e5%8c%96%e5%8f%8d%e5%ba%94%e6%96%b9%e6%b3%95%e5%ad%a6","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2021\/10\/org-lett-%ef%bc%9a%e8%8a%b3%e5%9f%ba%e7%a2%98%e4%b8%8e%e8%8b%af%e5%b9%b6%e5%91%8b%e5%96%83%e4%b9%8b%e9%97%b4%e7%9a%84c-h%e8%8a%b3%e5%9f%ba%e5%8c%96%e5%8f%8d%e5%ba%94%e6%96%b9%e6%b3%95%e5%ad%a6.html","title":{"rendered":"Org. Lett.\uff1a\u82b3\u57fa\u7898\u4e0e\u82ef\u5e76\u544b\u5583\u4e4b\u95f4\u7684C-H\u82b3\u57fa\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66"},"content":{"rendered":"

\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749<\/strong><\/p>\n

\u5bfc\u8bfb<\/h4>\n

\u8fd1\u65e5\uff0cWashington\u5927\u5b66\u7684C. K. Luscombe\u8bfe\u9898\u7ec4\u5728Org. Lett.<\/em>\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u5728\u5ba4\u6e29\u6761\u4ef6\u4e0b\u8fdb\u884c\u7684\u82ef\u5e76\u544b\u5583\u5316\u5408\u7269\u7684\u76f4\u63a5C-H\u82b3\u57fa\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002\u8fd9\u4e00\u5168\u65b0\u7684\u82b3\u57fa\u5316\u7b56\u7565\u5177\u6709\u4f18\u826f\u7684C-2\u533a\u57df\u9009\u62e9\u6027\uff0c\u5e76\u9009\u62e9\u5e02\u552e\u7684\u82b3\u57fa\u7898\u4f5c\u4e3a\u82b3\u57fa\u6e90\uff0c\u540c\u65f6\uff0c\u5177\u6709\u826f\u597d\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u3002\u53cd\u5e94\u673a\u7406\u7814\u7a76\u8868\u660e\uff0c\u901a\u8fc7\u82b3\u57fa\u5316\u8fc7\u7a0b\u5f62\u6210\u7684Heck\u578b\u6c27\u82b3\u57fa\u5316 (oxyarylation)\u4ea7\u7269\uff0c\u80fd\u591f\u4f5c\u4e3a\u94af\u78b3\u5316 (carbopalladation)\u4e2d\u95f4\u4f53\u5b58\u5728\u7684\u5173\u952e\u8bc1\u636e\u3002<\/p>\n

Room Temperature C-H Arylation of Benzofurans by Aryl Iodides
\nA. L. Mayhugh, C. K. Luscombe, Org. Lett<\/em>. ASAP doi: 10.1021\/acs.orglett.1c02397<\/u><\/a>.<\/u><\/p><\/blockquote>\n

\"\"<\/a><\/p>\n

\u6b63\u6587<\/h4>\n

\u82ef\u5e76\u544b\u5583\u53ca\u5176\u884d\u751f\u7269\u4f5c\u4e3a\u91cd\u8981\u7684\u7ed3\u6784\u5355\u5143\uff0c\u5e7f\u6cdb\u5b58\u5728\u4e8e\u836f\u7269\u4ee5\u53ca\u6750\u6599\u7b49\u5206\u5b50\u4e2d\u3002\u5176\u4e2d\uff0c\u03b1<\/em>-\u82b3\u57fa\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u662f\u6784\u5efa\u82ef\u5e76\u544b\u5583\u9aa8\u67b6\u7684\u91cd\u8981\u7b56\u7565\u3002\u540c\u65f6\uff0c\u4f20\u7edf\u7684\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\u7b56\u7565\uff0c\u76ee\u524d\u4ecd\u7136\u5e94\u7528\u8f83\u4e3a\u5e7f\u6cdb\u3002\u6b64\u5916\uff0c\u82ef\u5e76\u544b\u5583\u5e95\u7269\u7684\u76f4\u63a5C-H\u82b3\u57fa\u5316\u7b56\u7565\u5df2\u7ecf\u5f00\u59cb\u53d7\u5230\u5408\u6210\u5316\u5b66\u5bb6\u7684\u5173\u6ce8\u3002\u7136\u800c\uff0c\u4e0a\u8ff0C-H\u82b3\u57fa\u5316\u7b56\u7565\u4e2d\u5374\u5b58\u5728\u53cd\u5e94\u6e29\u5ea6\u8fc7\u9ad8\u4ee5\u53ca\u70ed\u654f\u6027\u5b98\u80fd\u56e2\u65e0\u6cd5\u6709\u6548\u517c\u5bb9\u7684\u95ee\u9898\uff0c\u4ece\u800c\u4f7f\u8fd9\u4e00\u7b56\u7565\u7684\u8fdb\u4e00\u6b65\u5e94\u7528\u53d7\u5230\u8f83\u5927\u9650\u5236[1]<\/sup>\u3002\u5c3d\u7ba1\u5c11\u6570\u8f83\u4e3a\u6e29\u548c\u7684C-H\u82b3\u57fa\u5316\u7b56\u7565\uff0c\u76ee\u524d\u5df2\u7ecf\u6709\u76f8\u5173\u7684\u6587\u732e\u62a5\u9053[2]<\/sup>\uff0c\u7136\u800c\uff0c\u540c\u6837\u5b58\u5728\u5ba4\u6e29\u6761\u4ef6\u4e0b\u53cd\u5e94\u901f\u7387\u7f13\u6162\u3001\u5e95\u7269\u5e94\u7528\u8303\u56f4\u8f83\u4e3a\u6709\u9650\u4ee5\u53ca\u91c7\u7528\u6613\u4e8e\u5206\u89e3\u5e76\u96be\u4ee5\u83b7\u5f97\u7684\u82b3\u9999\u91cd\u6c2e\u76d0\u7b49\u5c40\u9650\u3002\u4e0e\u6b64\u540c\u65f6\uff0c\u5c3d\u7ba1\u6d89\u53ca\u6742\u73af\u8054\u82b3\u57fa\u5316\u5408\u7269 (heterobiaryl)\u6784\u5efa\u7684\u5ba4\u6e29\u82b3\u57fa\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u5df2\u6709\u76f8\u5173\u7684\u7814\u7a76\u62a5\u9053\uff0c\u4f8b\u5982\u5432\u54da\u4ee5\u53ca\u82ef\u5e76\u567b\u5429\u5316\u5408\u7269\u7684C-H\u82b3\u57fa\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66[3]<\/sup>\u3002\u7136\u800c\uff0c\u5b9e\u73b0\u82ef\u5e76\u544b\u5583\u5316\u5408\u7269\u7684\u5ba4\u6e29\u76f4\u63a5\u82b3\u57fa\u5316\u53cd\u5e94\uff0c\u5219\u4ecd\u6709\u5f85\u8fdb\u4e00\u6b65\u7814\u7a76\u3002\u4e3a\u89e3\u51b3\u8fd9\u4e00\u95ee\u9898\uff0c\u672c\u6587\u4f5c\u8005\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u91c7\u7528\u82b3\u57fa\u7898\u4f5c\u4e3a\u82b3\u57fa\u6e90\uff0c\u8fdb\u884c\u7684\u82ef\u5e76\u544b\u5583\u5316\u5408\u7269\u7684C-2\u533a\u57df\u9009\u62e9\u6027\u82b3\u57fa\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002<\/p>\n

\u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u82ef\u5e76\u544b\u5583\u5316\u5408\u72691a<\/strong>\u4e0e\u7898\u82ef2a<\/strong>\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u4e86\u76f8\u5173\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Scheme 1)\u3002\u8fdb\u800c\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u7528Pd(OAc)2<\/sub>\u4f5c\u4e3a\u50ac\u5316\u5242\uff0cAg2<\/sub>O\u4f5c\u4e3a\u94f6\u76d0\u524d\u4f53\uff0c2-\u785d\u57fa\u82ef\u7532\u9178\u4f5c\u4e3a\u6dfb\u52a0\u5242\uff0c\u5728\u516d\u6c1f\u5f02\u4e19\u9187 (HFIP)\u6eb6\u5242\u4e2d\uff0c\u5ba4\u6e29\u6761\u4ef6\u4e0b\u8fdb\u884c\u53cd\u5e94\uff0c\u6700\u7ec8\u83b7\u5f9790%\u6536\u7387\u7684\u5076\u8054C-H\u82b3\u57fa\u5316\u4ea7\u72693a<\/strong>\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u9996\u5148\u5bf9\u82b3\u57fa\u7898\u5e95\u7269\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u8003\u5bdf (Scheme 2)\u3002\u7814\u7a76\u8868\u660e\uff0c\u4e00\u7cfb\u5217\u82b3\u57fa\u4e0d\u540c\u4f4d\u7f6e\u5e26\u6709\u4f9b\u7535\u5b50\u4e0e\u5438\u7535\u5b50\u57fa\u56e2\u53d6\u4ee3\u7684\u82b3\u57fa\u7898\u5e95\u7269\uff0c\u5747\u80fd\u591f\u8f83\u597d\u5730\u4e0e\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u517c\u5bb9\uff0c\u5e76\u4ee535-94%\u6536\u7387\u83b7\u5f97\u76f8\u5e94\u7684C-H\u82b3\u57fa\u5316\u4ea7\u72693a<\/strong>–3o<\/strong>\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8fd9\u4e00\u5168\u65b0\u7684C-H\u82b3\u57fa\u5316\u7b56\u7565\u5177\u6709\u826f\u597d\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\uff0c\u5bf9\u4e8e\u82b3\u57fa\u7898\u5e95\u7269\u4e2d\u5b58\u5728\u7684\u5364\u7d20\u53d6\u4ee3\u57fa\u3001\u9187\u7f9f\u57fa\u3001\u919b\u57fa\u4ee5\u53ca\u916f\u57fa\u7b49\uff0c\u5747\u80fd\u591f\u6709\u6548\u5730\u8fdb\u884c\u517c\u5bb9\u3002\u66f4\u4e3a\u6709\u8da3\u7684\u662f\uff0c\u5728\u9009\u62e92-\u7898\u82ef\u915a\u4f5c\u4e3a\u53cd\u5e94\u5e95\u7269\u65f6\uff0c\u80fd\u591f\u8fdb\u884c\u8fdb\u4e00\u6b65\u7684\u4e32\u8054\u53cd\u5e94\u8fc7\u7a0b\uff0c\u5e76\u4ee5\u8f83\u9ad8\u7684\u53cd\u5e94\u6536\u7387\u83b7\u5f97\u76f8\u5e94\u76844b,9b-\u4e8c\u6c22\u82ef\u5e76\u544b\u5583[3,2-b<\/em>]\u82ef\u5e76\u544b\u5583\u4ea7\u7269 (4<\/strong>)\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u5bf9\u82ef\u5e76\u544b\u5583\u5e95\u7269\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u8003\u5bdf (Scheme 3)\u3002\u7814\u7a76\u8868\u660e\uff0c\u5728\u82ef\u5e76\u544b\u5583\u5e95\u7269\u4e2d\u7684\u82b3\u57fa\u4e0d\u540c\u4f4d\u7f6e\u5177\u6709\u5f02\u4e19\u57fa\u3001\u6eb4\u3001\u7532\u6c27\u57fa\u4ee5\u53ca\u787c\u9178\u916f\u57fa\u56e2\u53d6\u4ee3\u65f6\uff0c\u5747\u80fd\u591f\u987a\u5229\u5730\u53c2\u4e0e\u4e0a\u8ff0\u7684C-H\u82b3\u57fa\u5316\u8fc7\u7a0b\uff0c\u5e76\u4ee541-74%\u7684\u6536\u7387\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u72693p<\/strong>–3s<\/strong>\u3002\u540c\u65f6\uff0c\u8be5\u5c0f\u7ec4\u53d1\u73b0\uff0c\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u5bf9\u4e8eC-3\u4f4d\u5e26\u6709\u7532\u57fa\u53d6\u4ee3\u7684\u82ef\u5e76\u544b\u5583\u5e95\u7269\uff0c\u540c\u6837\u80fd\u591f\u826f\u597d\u5730\u517c\u5bb9\uff0c\u5e76\u4ee582%\u7684\u53cd\u5e94\u6536\u7387\u83b7\u5f97\u76f8\u5e94C-H\u82b3\u57fa\u5316\u4ea7\u72693t<\/strong>\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8fd9\u4e00\u5168\u65b0\u7684C-H\u82b3\u57fa\u5316\u7b56\u7565\u540c\u6837\u80fd\u591f\u5e94\u7528\u4e8e\u76ae\u80a4\u75c5\u6cbb\u7597\u836f\u7269xanthotoxin\u884d\u751f\u72693u<\/strong>\u7684\u5408\u6210\u3002\u7136\u800c\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u89c2\u5bdf\u5230\uff0c\u5c06\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u5e94\u7528\u4e8e\u53cc\u7532\u57fa\u53d6\u4ee3\u7684\u544b\u5583\u5e95\u7269\u65f6\uff0c\u5219\u672a\u80fd\u83b7\u5f97\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u72693v<\/strong>\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u4e3a\u9610\u660e\u5408\u7406\u7684\u53cd\u5e94\u673a\u7406\uff0c\u4f5c\u8005\u8fdb\u884c\u4e00\u7cfb\u5217\u76f8\u5173\u7684\u5b9e\u9a8c\u7814\u7a76 (Scheme 4)\u3002\u9996\u5148\uff0c\u8be5\u5c0f\u7ec4\u5728\u4e0a\u8ff0\u6807\u51c6\u53cd\u5e94\u4f53\u7cfb\u4e2d\u5b58\u57282a<\/strong>\u6216\u65e02a<\/strong>\u5b58\u5728\u65f6\uff0c\u5206\u522b\u4e0e2d<\/em>–1a<\/strong>\u4ee5\u53ca3d<\/em>–1a<\/strong>\u8fdb\u884c\u76f8\u5173\u7684\u6c22\u6c18\u4ea4\u6362\u5b9e\u9a8c\u7814\u7a76 (Scheme 4a)\u3002\u5b9e\u9a8c\u4e2d\u4f5c\u8005\u89c2\u5bdf\u5230\uff0c\u4e0e\u901a\u8fc7\u534f\u540c\u91d1\u5c5e\u5316-\u53bb\u8d28\u5b50\u5316 (CMD)\u8def\u5f84\u8fdb\u884c\u7684Pd\u6216Ag\u5a92\u4ecb\u7684C-H\u6d3b\u5316\u8fc7\u7a0b\u7684\u9884\u6d4b\u76f8\u53cd\uff0c\u5728\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u6761\u4ef6\u4e0b\uff0c\u5747\u672a\u89c2\u5bdf\u5230\u76f8\u5e94\u7684\u6c22\u6c18\u7f6e\u4e71\u73b0\u8c61\u3002\u800c\u5728\u53cd\u5e94\u8fc7\u7a0b\u901a\u8fc7CMD\u673a\u7406\u8fdb\u884c\u7684\u60c5\u51b5\u4e0b\uff0c\u5982\u679cC-H\u6d3b\u5316\u8fc7\u7a0b\u4e3a\u51b3\u901f\u6b65\u9aa4\uff0c\u540c\u65f6\u53cd\u5e94\u8fc7\u7a0b\u53ef\u9006\uff0c\u5219\u80fd\u591f\u5728C-2\u4f4d\u7f6e\u89c2\u5bdf\u5230\u76f8\u5e94\u7684\u6c22\u6c18\u7f6e\u4e71\u73b0\u8c61\u3002\u5e76\u4e14\uff0c\u901a\u8fc7\u6c22\u6c18\u4ea4\u6362\u5b9e\u9a8c\u7684\u7814\u7a76\uff0c\u540c\u6837\u80fd\u591f\u8fdb\u4e00\u6b65\u6392\u9664\u975e\u51b3\u901f\u7684C-H\u6d3b\u5316\u8fc7\u7a0b\u4ee5\u53ca\u53ef\u9006\u7684CMD\u673a\u7406[<\/sup>4]-[5]<\/sup>\u3002<\/p>\n

\u4e4b\u540e\uff0c\u4e3a\u8fdb\u4e00\u6b65\u7814\u7a76\u53cd\u5e94\u673a\u7406\u8fc7\u7a0b\u4e2d\u7684\u9a71\u52a8\u56e0\u7d20\uff0c\u4f5c\u8005\u5bf9\u82ef\u5e76\u544b\u5583C-2\u4f4d\u7684KIE\u8fdb\u884c\u6df1\u5165\u7814\u7a76 (Scheme 4b)\u3002\u5b9e\u9a8c\u89c2\u5bdf\u5230C-2\u4f4d\u7684SKIE\u00a0(secondary KIE)\u6570\u503c\u4e3a1.15\uff0c\u8fdb\u800c\u8868\u660e\uff0c\u4e0a\u8ff0\u7684C-H\u82b3\u57fa\u5316\u8fc7\u7a0b\u65e0\u6cd5\u901a\u8fc7C-H\u6d3b\u5316\u4f5c\u4e3a\u51b3\u901f\u6b65\u9aa4\u7684CMD\u8def\u5f84\u8fdb\u884c\u3002\u9664CMD\u8def\u5f84\u4e4b\u5916\uff0cPd\u50ac\u5316C-H\u82b3\u57fa\u5316\u53cd\u5e94\u8fc7\u7a0b\u540c\u6837\u6d89\u53ca\u5176\u5b83\u7684\u673a\u7406\u8def\u5f84\uff0c\u4f8b\u5982Heck\u578b\u673a\u7406[<\/sup>6<\/sup>]<\/sup>\u4ee5\u53ca\u4eb2\u7535\u82b3\u9999\u53d6\u4ee3 (SE<\/sub>Ar)\u673a\u7406[<\/sup>7<\/sup>]<\/sup>\u3002\u5176\u4e2d\uff0c\u82ef\u5e76\u544b\u5583\u7684SE<\/sub>Ar\u53cd\u5e94\u8fc7\u7a0b\uff0c\u80fd\u591f\u9009\u62e9\u6027\u5730\u5728C-2\u4f4d\u7f6e\u8fdb\u884c\uff0c\u8fd9\u4e0e\u4eb2\u7535\u785d\u5316\u4ee5\u53ca\u4eb2\u7535\u9170\u5316\u8fc7\u7a0b\u4e2d\u6240\u89c2\u5bdf\u5230\u7684\u533a\u57df\u9009\u62e9\u6027\u4e00\u81f4\u3002\u5e76\u4e14C-2\u4f4d\u7f6e\u7684\u9009\u62e9\u6027\uff0c\u901a\u8fc7\u5177\u6709\u7a33\u5b9a\u5316\u82c4\u57fa\u78b3\u6b63\u79bb\u5b50\u7279\u6027\u7684\u03c3<\/em>-\u914d\u5408\u7269\u4e2d\u95f4\u4f53\u8fdb\u884c\u9a71\u52a8\uff0c\u8fdb\u800c\u5b9e\u73b0\u82b3\u57fa\u5316\u8fc7\u7a0b\u4e2d\u9884\u671f\u7684\u533a\u57df\u9009\u62e9\u6027\u3002\u7136\u800c\uff0cC-2\u4f4d\u7f6e\u89c2\u5bdf\u5230\u7684\u6b63\u7684SKIE\u6570\u503c\uff0c\u5e76\u65e0\u6cd5\u8868\u660e\u5728C-2\u4f4d\u7f6e\u4e2d\u5b58\u5728\u76f8\u5173\u7684\u94af\u5316 (palladation)\u8fc7\u7a0b\u3002\u5373\u7531\u4e8e\u53bb\u8d28\u5b50\u5316\u901f\u7387\u4e0e\u82b3\u57fa\u6b63\u79bb\u5b50\u00a0(arenium ion)\u7684\u5f62\u6210\u901f\u7387\u76f8\u5f53\uff0c\u56e0\u6b64\uff0c\u901a\u5e38\u60c5\u51b5\u4e0b\uff0c\u82b3\u9999\u4eb2\u7535\u53d6\u4ee3\u8fc7\u7a0b\u7684KIE\u6570\u503c\u8f83\u5c0f\uff0c\u751a\u81f3\u65e0\u6cd5\u89c2\u5bdf\u5230KIE\u7684\u5b58\u5728\u3002\u7531\u6b64\uff0c\u4f5c\u8005\u5047\u8bbe\uff0cC-2\u4f4d\u7684\u94af\u5316\u8fc7\u7a0b\uff0c\u4ecd\u7136\u53ef\u80fd\u901a\u8fc7SE<\/sub>Ar\u673a\u7406\u8fdb\u884c\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u63a5\u4e0b\u6765\uff0c\u8be5\u5c0f\u7ec4\u901a\u8fc72-\u7898\u82ef\u915a\u73af\u5316\uff0c\u5f62\u6210\u4ea7\u72694<\/strong>\u7684\u53cd\u5e94\u8fc7\u7a0b\uff0c\u8fdb\u800c\u8bc1\u5b9e\u5177\u6709sp3<\/sup>\u78b3\u4e2d\u5fc3\u7684C-3-\u94af\u914d\u5408\u7269\u7684\u5b58\u5728\u3002\u5e76\u4e14\uff0c\u4ea7\u72694<\/strong>\u7684\u5f62\u6210\u8fc7\u7a0b\uff0c\u4e0e\u9884\u671f\u7684Heck\u578b\u6c27\u82b3\u57fa\u5316\u8fc7\u7a0b\u76f8\u4e00\u81f4\u3002\u5176\u4e2d\uff0c\u90bb\u8fd1\u7684\u7f9f\u57fa\u80fd\u591f\u8fdb\u4e00\u6b65\u53d6\u4ee3\u82ef\u5e76\u544b\u5583\u73af\u4e2d\u7684\u94af\u57fa\u56e2 (Scheme S1)\u3002\u76f8\u53cd\u5730\uff0c\u901a\u8fc7SE<\/sub>Ar\u673a\u7406\u8fdb\u884c\u7684C-2\u94af\u5316\u8fc7\u7a0b\u4e2d\uff0c\u5728C-3\u4f4d\u7f6e\u80fd\u591f\u5f62\u6210\u76f8\u5e94\u7684\u78b3\u6b63\u79bb\u5b50\u4e2d\u5fc3 (Scheme S1)\u3002\u540c\u65f6\uff0c\u5728\u9178\u6027\u6761\u4ef6\u4e0b\uff0c2-\u7898\u82ef\u915a\u4e2d\u7684\u7f9f\u57fa\u5b98\u80fd\u56e2\u65e0\u6cd5\u4e0e\u78b3\u6b63\u79bb\u5b50\u4e2d\u5fc3\u8fdb\u884c\u6210\u952e\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u8003\u8651\u5230\uff0c\u540c\u6837\u53ef\u80fd\u5b58\u5728\u4e00\u79cd\u4e0e\u82b3\u57fa\u5316\u8fc7\u7a0b\u76f8\u4e92\u72ec\u7acb\u7684\u4e8c\u7ea7C-O\u952e\u7684\u5f62\u6210\u8fc7\u7a0b\u3002\u800c\u4e14\uff0c\u5373\u4f7f\u5728\u5e95\u7269\u5b8c\u5168\u8f6c\u5316\u4e4b\u524d\uff0c\u5c06\u53cd\u5e94\u8fc7\u7a0b\u505c\u6b62\uff0c\u540c\u6837\u65e0\u6cd5\u83b7\u5f97\u76f8\u5e94\u7684\u82b3\u57fa\u5316\u4ea7\u7269 (3h<\/strong>)\u3002\u5e76\u4e14\uff0c\u5bf9\u4e8e\u5176\u4ed6\u672a\u4fdd\u62a4\u7684\u9187\u5e95\u7269\uff0c\u5728\u4e0a\u8ff0\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u4e0b\u7684\u7a33\u5b9a\u6027\u7684\u76f8\u5173\u7814\u7a76\uff0c\u540c\u6837\u65e0\u6cd5\u8bc1\u5b9eSE<\/sub>Ar\u8fc7\u7a0b\u5728C-O\u73af\u5316\u6b65\u9aa4\u4e4b\u524d\u8fdb\u884c\u3002\u540c\u65f6\uff0c\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u89c2\u5bdf\u4e0ePd\u50ac\u5316\u7684\u70ef\u57fa\u5316\u5408\u7269\u7684\u6c27\u82b3\u57fa\u5316\/C-H\u5b98\u80fd\u56e2\u5316\u8fc7\u7a0b\u4e00\u81f4\uff0c\u8fdb\u800c\u8868\u660e\u8fd9\u4e00\u5168\u65b0\u7684C-H\u82b3\u57fa\u5316\u8fc7\u7a0b\u4e0eHeck\u5316\u5b66\u4e4b\u95f4\u5177\u6709\u76f8\u4f3c\u6027\u3002\u800c\u4e14\uff0c\u901a\u8fc7\u4e0a\u8ff0\u5b9e\u9a8c\u89c2\u5bdf\uff0c\u80fd\u591f\u8fdb\u4e00\u6b65\u6392\u9664C-2\u4f4d\u82b3\u57fa\u5316\u8fc7\u7a0b\u901a\u8fc7SE<\/sub>Ar\u673a\u7406\u8fdb\u884c\u7684\u53ef\u80fd\u6027\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u6700\u540e\uff0c\u7ed3\u5408\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u7814\u7a76\uff0c\u4f5c\u8005\u5047\u8bbe\u8fd9\u4e00\u5168\u65b0\u7684C-H\u82b3\u57fa\u5316\u8fc7\u7a0b\u901a\u8fc7Heck\u578b\u673a\u7406\u8def\u5f84\u8fdb\u884c (Scheme 5)\u3002\u9996\u5148\uff0c\u901a\u8fc7\u82b3\u57fa\u7898\u4e0ePd(0)\u4e4b\u95f4\u7684\u6c27\u5316\u52a0\u6210\u8fc7\u7a0b\uff0c\u5f62\u6210\u4e2d\u95f4\u4f53II<\/strong>\uff0c\u4e4b\u540e\uff0c\u4e2d\u95f4\u4f53II<\/strong>\u4e0e\u539f\u4f4d\u5f62\u6210\u7684\u7fa7\u9178\u94f6\u76d0\u4e4b\u95f4\u901a\u8fc7\u5364\u79bb\u5b50\u652b\u53d6 (halide abstraction)\u6b65\u9aa4\uff0c\u5f62\u6210\u5177\u6709\u66f4\u9ad8\u53cd\u5e94\u6d3b\u6027\u7684\u94af\u91d1\u5c5e\u4e2d\u5fc3\uff0c\u540c\u65f6\uff0c\u901a\u8fc7\u94af\u91d1\u5c5e\u4e2d\u5fc3\u4e2d\u65b0\u5f15\u5165\u7684\u7fa7\u57fa\u8d1f\u79bb\u5b50\u914d\u4f53\u7684\u8fdb\u4e00\u6b65\u89e3\u79bb\uff0c\u5f62\u6210\u94af\u9633\u79bb\u5b50\u914d\u5408\u7269\u00a0III<\/b><\/strong>\u3002\u63a5\u4e0b\u6765\uff0c1a<\/strong>\u4e0e\u94af\u9633\u79bb\u5b50\u914d\u5408\u7269\u00a0III<\/b><\/strong>\u4e4b\u95f4\u7ecf\u5386\u94af\u78b3\u5316 (carbopalladation)\u6b65\u9aa4\uff0c\u5f62\u6210\u4e2d\u95f4\u4f53IV<\/strong>\uff0c\u5e76\u8fdb\u4e00\u6b65\u901a\u8fc7\u78b1\u8f85\u52a9\u7684anti-\u03b2<\/em>-\u6d88\u9664\u6b65\u9aa4\uff0c\u8fdb\u800c\u83b7\u5f97\u76ee\u6807\u4ea7\u72693<\/strong>\uff0c\u540c\u65f6\uff0c\u4f7fPd(0)\u50ac\u5316\u5242\u518d\u751f\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u5047\u8bbe\uff0c\u5364\u79bb\u5b50\u652b\u53d6\u4ee5\u53ca\u540e\u7eed\u7684\u914d\u4f53\u89e3\u79bb\u8fc7\u7a0b\uff0c\u662f\u4e0a\u8ff0C-H\u82b3\u57fa\u5316\u53cd\u5e94\u8fc7\u7a0b\u80fd\u591f\u5728\u5ba4\u6e29\u6761\u4ef6\u4e0b\u987a\u5229\u8fdb\u884c\u7684\u5173\u952e\u3002\u6b64\u5916\uff0c\u9664\u901a\u8fc7\u6c22\u952e\u4f5c\u7528[<\/sup>8<\/sup>]<\/sup>\uff0c\u4f7f\u6d3b\u6027\u94af\u914d\u5408\u7269\u7a33\u5b9a\u5316\u4e4b\u5916\uff0cHFIP\u540c\u6837\u53ef\u80fd\u4e0e\u7fa7\u9178\u94f6\u4e4b\u95f4\u8fdb\u884c\u76f8\u5e94\u7684\u9178\u78b1\u4ea4\u6362\u8fc7\u7a0b[<\/sup>9<\/sup>]<\/sup>\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u603b\u7ed3<\/h4>\n

Washington\u5927\u5b66\u7684C. K. Luscombe\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u82ef\u5e76\u544b\u5583\u884d\u751f\u7269\u7684\u533a\u57df\u9009\u62e9\u6027C-2\u82b3\u57fa\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002\u5e76\u4e14\uff0c\u8fd9\u4e00\u5168\u65b0\u7684C-H\u82b3\u57fa\u5316\u7b56\u7565\u5177\u6709\u53cd\u5e94\u6761\u4ef6\u6e29\u548c\u4ee5\u53ca\u6781\u4e3a\u4f18\u826f\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u7b49\u4f18\u52bf\u3002\u540c\u65f6\uff0c\u4f5c\u8005\u8bbe\u60f3\uff0c\u4e0a\u8ff0\u7684C-H\u82b3\u57fa\u5316\u8fc7\u7a0b\u901a\u8fc7Heck\u578b\u82b3\u57fa\u5316\u673a\u7406\u8fdb\u884c\u3002<\/p>\n

\u53c2\u8003\u6587\u732e<\/b><\/strong><\/h4>\n[1]\u00a0(a) S. C. Yin, Q. Zhou, X. Y. Zhao, L. X. Shao, J. Org.<\/em>\u00a0<\/em>Chem.<\/em>\u00a02015<\/strong>, 80, 891.\u00a0doi:\u00a010.1021\/acs.joc.5b01544<\/u><\/a>.<\/u><\/p>\n

(b) J. Cao, Z. L. Chen, S. M. Li, G. F. Zhu, Y. Y. Yang, C. Wang,\u00a0W. Z. Chen, J. T. Wang, J. Q. Zhang, L. Tang, Eur. J. Org. Chem.<\/em>\u00a02018<\/strong>, 22<\/em>, 2774.\u00a0doi:\u00a010.1002\/ejoc.201800374<\/u><\/a>.<\/u><\/p>\n

(c) S. Mao, X. Shi, J. F. Soul\u00e9, H. Doucet, Eur. J. Org. Chem.<\/em>\u00a02020<\/strong>, 2020<\/em>, 91.\u00a0doi:\u00a010.1002\/ejoc.201901561<\/u><\/a>.<\/u><\/p>\n[2] (a) H. P. L. Gemoets, I. Kalvet, A. V. Nyuchev, N. Erdmann,\u00a0V. Hessel, F. Schoenebeck, T. No\u00ebl,\u00a0<\/em>Chem.<\/em>\u00a0<\/em>Sci.<\/em>\u00a02017<\/strong>, 8<\/em>, 1046.\u00a0doi:\u00a010.1039\/C6SC02595A<\/u><\/a>.<\/u><\/p>\n

(b) A. F. P. Biajoli, E. T. Da Penha, C. R. D. Correia, RSC Adv. <\/em>2012<\/strong>, 2<\/em>,\u00a011930.\u00a0doi:\u00a010.1039\/C2RA22213B<\/u><\/a>.<\/u><\/p>\n

(c) Z. Xu, Y. Xu, H. Lu, T. Yang, X. Lin, L. Shao, F. Ren,\u00a0Tetrahedron<\/em>\u00a02015<\/strong>, 71<\/em>, 2616.\u00a0doi:\u00a010.1016\/j.tet.2015.03.051<\/u><\/a>.<\/u><\/p>\n[3] (a) N. Lebrasseur, I. Larrosa, J. Am.<\/em>\u00a0<\/em>Chem. Soc<\/em>. 2008<\/strong>, 130<\/em>, 2926.\u00a0doi:\u00a010.1021\/ja710731a<\/u><\/a>.<\/u><\/p>\n

(b) C. Colletto, A. Panigrahi, J. Fern\u00e1ndez-Casado, I. Larrosa,\u00a0J. Am. Chem. Soc. <\/em>2018<\/strong>, 140<\/em>,\u00a09638.\u00a0doi:\u00a010.1021\/jacs.8b05361<\/u><\/a>.<\/u><\/p>\n[4] S. I. Gorelsky, D. Lapointe, K. Fagnou,\u00a0J. Org.<\/i><\/em>\u00a0<\/i><\/em>Chem.<\/i><\/em>\u00a02012<\/b><\/strong>, 77<\/i><\/em>, 658. doi:\u00a010.1021\/jo202342q<\/u><\/a>.<\/u><\/p>\n[5]\u00a0M. D. Lotz, N. M. Camasso, A. J. Canty, M. S.\u00a0Sanford, Organometallics<\/i><\/em>\u00a02017<\/b><\/strong>, 36<\/i><\/em>, 165.\u00a0doi:\u00a010.1021\/acs.organomet.6b00437<\/u><\/a>.<\/u><\/p>\n[6]\u00a0C. Colletto, S. Islam, F. Juli\u00e1-Hern\u00e1ndez, I. Larrosa, J. Am.<\/em>\u00a0<\/em>Chem. Soc.<\/em>\u00a02016<\/strong>, 138<\/em>, 1677.\u00a0doi:\u00a010.1021\/jacs.5b12242<\/u><\/a>.<\/u><\/p>\n[7]\u00a0S. I. Gorelsky, D. Lapointe, K. Fagnou, J. Org.<\/em>\u00a0<\/em>Chem.<\/em>\u00a02012<\/strong>, 77<\/em>, 658.\u00a0doi:\u00a010.1021\/jo202342q<\/u><\/a>.<\/u><\/p>\n[8] T. Bhattacharya, A. Ghosh, D. Maiti, Chem. Sci.<\/i><\/em>\u00a02021<\/b><\/strong>, 12<\/i><\/em>, 3857.\u00a0doi:\u00a010.1039\/D0SC06937J<\/u><\/a>.<\/u><\/p>\n[9]\u00a0C. Colletto, S. Islam, F. Juli\u00e1-Hern\u00e1ndez, I. Larrosa, J. Am. Chem. Soc.<\/i><\/em>\u00a02016<\/b><\/strong>, 138<\/i><\/em>, 1677.\u00a0doi:\u00a010.1021\/jacs.5b12242<\/u><\/a>.<\/u><\/p>\n

 <\/p>\n

\u672c\u6587\u7248\u6743\u5c5e\u4e8e\u00a0Chem-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\uff01<\/strong><\/p>\n","protected":false},"excerpt":{"rendered":"\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749 \u5bfc\u8bfb \u8fd1\u65e5\uff0cWashington\u5927\u5b66\u7684C. K. Luscombe\u8bfe\u9898\u7ec4\u5728Org. Lett.\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u5728\u5ba4\u6e29\u6761\u4ef6\u4e0b\u8fdb\u884c\u7684\u82ef\u5e76\u544b\u5583\u5316\u5408\u7269\u7684\u76f4\u63a5C-H\u82b3\u57fa\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002\u8fd9\u4e00\u5168\u65b0\u7684\u82b3\u57fa\u5316\u7b56\u7565\u5177\u6709\u4f18\u826f\u7684C-2\u533a\u57df\u9009\u62e9\u6027\uff0c\u5e76\u9009\u62e9\u5e02\u552e\u7684\u82b3\u57fa\u7898\u4f5c\u4e3a\u82b3\u57fa\u6e90\uff0c\u540c\u65f6\uff0c\u5177\u6709\u826f\u597d\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u3002\u53cd\u5e94\u673a\u7406\u7814\u7a76\u8868\u660e\uff0c\u901a\u8fc7\u82b3\u57fa\u5316\u8fc7\u7a0b\u5f62\u6210\u7684Heck\u578b\u6c27\u82b3\u57fa\u5316 (oxyarylation)\u4ea7\u7269\uff0c\u80fd\u591f\u4f5c\u4e3a\u94af\u78b3\u5316 (carbopalladation)\u4e2d\u95f4\u4f53\u5b58\u5728\u7684\u5173\u952e\u8bc1\u636e\u3002 Room Temperature C-H Arylation of Benzofurans by Aryl Iodides A. L. Mayhugh, C. K. Luscombe, Org. Lett. ASAP doi: 10.1021\/acs.orglett.1c02397. \u6b63\u6587 \u82ef\u5e76\u544b\u5583\u53ca\u5176\u884d\u751f\u7269\u4f5c\u4e3a\u91cd\u8981\u7684\u7ed3\u6784\u5355\u5143\uff0c\u5e7f\u6cdb\u5b58\u5728\u4e8e\u836f\u7269\u4ee5\u53ca\u6750\u6599\u7b49\u5206\u5b50\u4e2d\u3002\u5176\u4e2d\uff0c\u03b1-\u82b3\u57fa\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u662f\u6784\u5efa\u82ef\u5e76\u544b\u5583\u9aa8\u67b6\u7684\u91cd\u8981\u7b56\u7565\u3002\u540c\u65f6\uff0c\u4f20\u7edf\u7684\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\u7b56\u7565\uff0c\u76ee\u524d\u4ecd\u7136\u5e94\u7528\u8f83\u4e3a\u5e7f\u6cdb\u3002\u6b64\u5916\uff0c\u82ef\u5e76\u544b\u5583\u5e95\u7269\u7684\u76f4\u63a5C-H\u82b3\u57fa\u5316\u7b56\u7565\u5df2\u7ecf\u5f00\u59cb\u53d7\u5230\u5408\u6210\u5316\u5b66\u5bb6\u7684\u5173\u6ce8\u3002\u7136\u800c\uff0c\u4e0a\u8ff0C-H\u82b3\u57fa\u5316\u7b56\u7565\u4e2d\u5374\u5b58\u5728\u53cd\u5e94\u6e29\u5ea6\u8fc7\u9ad8\u4ee5\u53ca\u70ed\u654f\u6027\u5b98\u80fd\u56e2\u65e0\u6cd5\u6709\u6548\u517c\u5bb9\u7684\u95ee\u9898\uff0c\u4ece\u800c\u4f7f\u8fd9\u4e00\u7b56\u7565\u7684\u8fdb\u4e00\u6b65\u5e94\u7528\u53d7\u5230\u8f83\u5927\u9650\u5236[1]\u3002\u5c3d\u7ba1\u5c11\u6570\u8f83\u4e3a\u6e29\u548c\u7684C-H\u82b3\u57fa\u5316\u7b56\u7565\uff0c\u76ee\u524d\u5df2\u7ecf\u6709\u76f8\u5173\u7684\u6587\u732e\u62a5\u9053[2]\uff0c\u7136\u800c\uff0c\u540c\u6837\u5b58\u5728\u5ba4\u6e29\u6761\u4ef6\u4e0b\u53cd\u5e94\u901f\u7387\u7f13\u6162\u3001\u5e95\u7269\u5e94\u7528\u8303\u56f4\u8f83\u4e3a\u6709\u9650\u4ee5\u53ca\u91c7\u7528\u6613\u4e8e\u5206\u89e3\u5e76\u96be\u4ee5\u83b7\u5f97\u7684\u82b3\u9999\u91cd\u6c2e\u76d0\u7b49\u5c40\u9650\u3002\u4e0e\u6b64\u540c\u65f6\uff0c\u5c3d\u7ba1\u6d89\u53ca\u6742\u73af\u8054\u82b3\u57fa\u5316\u5408\u7269 (heterobiaryl)\u6784\u5efa\u7684\u5ba4\u6e29\u82b3\u57fa\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u5df2\u6709\u76f8\u5173\u7684\u7814\u7a76\u62a5\u9053\uff0c\u4f8b\u5982\u5432\u54da\u4ee5\u53ca\u82ef\u5e76\u567b\u5429\u5316\u5408\u7269\u7684C-H\u82b3\u57fa\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66[3]\u3002\u7136\u800c\uff0c\u5b9e\u73b0\u82ef\u5e76\u544b\u5583\u5316\u5408\u7269\u7684\u5ba4\u6e29\u76f4\u63a5\u82b3\u57fa\u5316\u53cd\u5e94\uff0c\u5219\u4ecd\u6709\u5f85\u8fdb\u4e00\u6b65\u7814\u7a76\u3002\u4e3a\u89e3\u51b3\u8fd9\u4e00\u95ee\u9898\uff0c\u672c\u6587\u4f5c\u8005\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u91c7\u7528\u82b3\u57fa\u7898\u4f5c\u4e3a\u82b3\u57fa\u6e90\uff0c\u8fdb\u884c\u7684\u82ef\u5e76\u544b\u5583\u5316\u5408\u7269\u7684C-2\u533a\u57df\u9009\u62e9\u6027\u82b3\u57fa\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002 \u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u82ef\u5e76\u544b\u5583\u5316\u5408\u72691a\u4e0e\u7898\u82ef2a\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u4e86\u76f8\u5173\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Scheme 1)\u3002\u8fdb\u800c\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u7528Pd(OAc)2\u4f5c\u4e3a\u50ac\u5316\u5242\uff0cAg2O\u4f5c\u4e3a\u94f6\u76d0\u524d\u4f53\uff0c2-\u785d\u57fa\u82ef\u7532\u9178\u4f5c\u4e3a\u6dfb\u52a0\u5242\uff0c\u5728\u516d\u6c1f\u5f02\u4e19\u9187 (HFIP)\u6eb6\u5242\u4e2d\uff0c\u5ba4\u6e29\u6761\u4ef6\u4e0b\u8fdb\u884c\u53cd\u5e94\uff0c\u6700\u7ec8\u83b7\u5f9790%\u6536\u7387\u7684\u5076\u8054C-H\u82b3\u57fa\u5316\u4ea7\u72693a\u3002 \u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u9996\u5148\u5bf9\u82b3\u57fa\u7898\u5e95\u7269\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u8003\u5bdf (Scheme 2)\u3002\u7814\u7a76\u8868\u660e\uff0c\u4e00\u7cfb\u5217\u82b3\u57fa\u4e0d\u540c\u4f4d\u7f6e\u5e26\u6709\u4f9b\u7535\u5b50\u4e0e\u5438\u7535\u5b50\u57fa\u56e2\u53d6\u4ee3\u7684\u82b3\u57fa\u7898\u5e95\u7269\uff0c\u5747\u80fd\u591f\u8f83\u597d\u5730\u4e0e\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u517c\u5bb9\uff0c\u5e76\u4ee535-94%\u6536\u7387\u83b7\u5f97\u76f8\u5e94\u7684C-H\u82b3\u57fa\u5316\u4ea7\u72693a–3o\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8fd9\u4e00\u5168\u65b0\u7684C-H\u82b3\u57fa\u5316\u7b56\u7565\u5177\u6709\u826f\u597d\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\uff0c\u5bf9\u4e8e\u82b3\u57fa\u7898\u5e95\u7269\u4e2d\u5b58\u5728\u7684\u5364\u7d20\u53d6\u4ee3\u57fa\u3001\u9187\u7f9f\u57fa\u3001\u919b\u57fa\u4ee5\u53ca\u916f\u57fa\u7b49\uff0c\u5747\u80fd\u591f\u6709\u6548\u5730\u8fdb\u884c\u517c\u5bb9\u3002\u66f4\u4e3a\u6709\u8da3\u7684\u662f\uff0c\u5728\u9009\u62e92-\u7898\u82ef\u915a\u4f5c\u4e3a\u53cd\u5e94\u5e95\u7269\u65f6\uff0c\u80fd\u591f\u8fdb\u884c\u8fdb\u4e00\u6b65\u7684\u4e32\u8054\u53cd\u5e94\u8fc7\u7a0b\uff0c\u5e76\u4ee5\u8f83\u9ad8\u7684\u53cd\u5e94\u6536\u7387\u83b7\u5f97\u76f8\u5e94\u76844b,9b-\u4e8c\u6c22\u82ef\u5e76\u544b\u5583[3,2-b]\u82ef\u5e76\u544b\u5583\u4ea7\u7269 (4)\u3002 \u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u5bf9\u82ef\u5e76\u544b\u5583\u5e95\u7269\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u8003\u5bdf (Scheme 3)\u3002\u7814\u7a76\u8868\u660e\uff0c\u5728\u82ef\u5e76\u544b\u5583\u5e95\u7269\u4e2d\u7684\u82b3\u57fa\u4e0d\u540c\u4f4d\u7f6e\u5177\u6709\u5f02\u4e19\u57fa\u3001\u6eb4\u3001\u7532\u6c27\u57fa\u4ee5\u53ca\u787c\u9178\u916f\u57fa\u56e2\u53d6\u4ee3\u65f6\uff0c\u5747\u80fd\u591f\u987a\u5229\u5730\u53c2\u4e0e\u4e0a\u8ff0\u7684C-H\u82b3\u57fa\u5316\u8fc7\u7a0b\uff0c\u5e76\u4ee541-74%\u7684\u6536\u7387\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u72693p–3s\u3002\u540c\u65f6\uff0c\u8be5\u5c0f\u7ec4\u53d1\u73b0\uff0c\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u5bf9\u4e8eC-3\u4f4d\u5e26\u6709\u7532\u57fa\u53d6\u4ee3\u7684\u82ef\u5e76\u544b\u5583\u5e95\u7269\uff0c\u540c\u6837\u80fd\u591f\u826f\u597d\u5730\u517c\u5bb9\uff0c\u5e76\u4ee582%\u7684\u53cd\u5e94\u6536\u7387\u83b7\u5f97\u76f8\u5e94C-H\u82b3\u57fa\u5316\u4ea7\u72693t\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8fd9\u4e00\u5168\u65b0\u7684C-H\u82b3\u57fa\u5316\u7b56\u7565\u540c\u6837\u80fd\u591f\u5e94\u7528\u4e8e\u76ae\u80a4\u75c5\u6cbb\u7597\u836f\u7269xanthotoxin\u884d\u751f\u72693u\u7684\u5408\u6210\u3002\u7136\u800c\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u89c2\u5bdf\u5230\uff0c\u5c06\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u5e94\u7528\u4e8e\u53cc\u7532\u57fa\u53d6\u4ee3\u7684\u544b\u5583\u5e95\u7269\u65f6\uff0c\u5219\u672a\u80fd\u83b7\u5f97\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u72693v\u3002 \u4e3a\u9610\u660e\u5408\u7406\u7684\u53cd\u5e94\u673a\u7406\uff0c\u4f5c\u8005\u8fdb\u884c\u4e00\u7cfb\u5217\u76f8\u5173\u7684\u5b9e\u9a8c\u7814\u7a76 (Scheme 4)\u3002\u9996\u5148\uff0c\u8be5\u5c0f\u7ec4\u5728\u4e0a\u8ff0\u6807\u51c6\u53cd\u5e94\u4f53\u7cfb\u4e2d\u5b58\u57282a\u6216\u65e02a\u5b58\u5728\u65f6\uff0c\u5206\u522b\u4e0e2d–1a\u4ee5\u53ca3d–1a\u8fdb\u884c\u76f8\u5173\u7684\u6c22\u6c18\u4ea4\u6362\u5b9e\u9a8c\u7814\u7a76 (Scheme 4a)\u3002\u5b9e\u9a8c\u4e2d\u4f5c\u8005\u89c2\u5bdf\u5230\uff0c\u4e0e\u901a\u8fc7\u534f\u540c\u91d1\u5c5e\u5316-\u53bb\u8d28\u5b50\u5316 (CMD)\u8def\u5f84\u8fdb\u884c\u7684Pd\u6216Ag\u5a92\u4ecb\u7684C-H\u6d3b\u5316\u8fc7\u7a0b\u7684\u9884\u6d4b\u76f8\u53cd\uff0c\u5728\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u6761\u4ef6\u4e0b\uff0c\u5747\u672a\u89c2\u5bdf\u5230\u76f8\u5e94\u7684\u6c22\u6c18\u7f6e\u4e71\u73b0\u8c61\u3002\u800c\u5728\u53cd\u5e94\u8fc7\u7a0b\u901a\u8fc7CMD\u673a\u7406\u8fdb\u884c\u7684\u60c5\u51b5\u4e0b\uff0c\u5982\u679cC-H\u6d3b\u5316\u8fc7\u7a0b\u4e3a\u51b3\u901f\u6b65\u9aa4\uff0c\u540c\u65f6\u53cd\u5e94\u8fc7\u7a0b\u53ef\u9006\uff0c\u5219\u80fd\u591f\u5728C-2\u4f4d\u7f6e\u89c2\u5bdf\u5230\u76f8\u5e94\u7684\u6c22\u6c18\u7f6e\u4e71\u73b0\u8c61\u3002\u5e76\u4e14\uff0c\u901a\u8fc7\u6c22\u6c18\u4ea4\u6362\u5b9e\u9a8c\u7684\u7814\u7a76\uff0c\u540c\u6837\u80fd\u591f\u8fdb\u4e00\u6b65\u6392\u9664\u975e\u51b3\u901f\u7684C-H\u6d3b\u5316\u8fc7\u7a0b\u4ee5\u53ca\u53ef\u9006\u7684CMD\u673a\u7406[4]-[5]\u3002 \u4e4b\u540e\uff0c\u4e3a\u8fdb\u4e00\u6b65\u7814\u7a76\u53cd\u5e94\u673a\u7406\u8fc7\u7a0b\u4e2d\u7684\u9a71\u52a8\u56e0\u7d20\uff0c\u4f5c\u8005\u5bf9\u82ef\u5e76\u544b\u5583C-2\u4f4d\u7684KIE\u8fdb\u884c\u6df1\u5165\u7814\u7a76 (Scheme 4b)\u3002\u5b9e\u9a8c\u89c2\u5bdf\u5230C-2\u4f4d\u7684SKIE\u00a0(secondary KIE)\u6570\u503c\u4e3a1.15\uff0c\u8fdb\u800c\u8868\u660e\uff0c\u4e0a\u8ff0\u7684C-H\u82b3\u57fa\u5316\u8fc7\u7a0b\u65e0\u6cd5\u901a\u8fc7C-H\u6d3b\u5316\u4f5c\u4e3a\u51b3\u901f\u6b65\u9aa4\u7684CMD\u8def\u5f84\u8fdb\u884c\u3002\u9664CMD\u8def\u5f84\u4e4b\u5916\uff0cPd\u50ac\u5316C-H\u82b3\u57fa\u5316\u53cd\u5e94\u8fc7\u7a0b\u540c\u6837\u6d89\u53ca\u5176\u5b83\u7684\u673a\u7406\u8def\u5f84\uff0c\u4f8b\u5982Heck\u578b\u673a\u7406[6]\u4ee5\u53ca\u4eb2\u7535\u82b3\u9999\u53d6\u4ee3 (SEAr)\u673a\u7406[7]\u3002\u5176\u4e2d\uff0c\u82ef\u5e76\u544b\u5583\u7684SEAr\u53cd\u5e94\u8fc7\u7a0b\uff0c\u80fd\u591f\u9009\u62e9\u6027\u5730\u5728C-2\u4f4d\u7f6e\u8fdb\u884c\uff0c\u8fd9\u4e0e\u4eb2\u7535\u785d\u5316\u4ee5\u53ca\u4eb2\u7535\u9170\u5316\u8fc7\u7a0b\u4e2d\u6240\u89c2\u5bdf\u5230\u7684\u533a\u57df\u9009\u62e9\u6027\u4e00\u81f4\u3002\u5e76\u4e14C-2\u4f4d\u7f6e\u7684\u9009\u62e9\u6027\uff0c\u901a\u8fc7\u5177\u6709\u7a33\u5b9a\u5316\u82c4\u57fa\u78b3\u6b63\u79bb\u5b50\u7279\u6027\u7684\u03c3-\u914d\u5408\u7269\u4e2d\u95f4\u4f53\u8fdb\u884c\u9a71\u52a8\uff0c\u8fdb\u800c\u5b9e\u73b0\u82b3\u57fa\u5316\u8fc7\u7a0b\u4e2d\u9884\u671f\u7684\u533a\u57df\u9009\u62e9\u6027\u3002\u7136\u800c\uff0cC-2\u4f4d\u7f6e\u89c2\u5bdf\u5230\u7684\u6b63\u7684SKIE\u6570\u503c\uff0c\u5e76\u65e0\u6cd5\u8868\u660e\u5728C-2\u4f4d\u7f6e\u4e2d\u5b58\u5728\u76f8\u5173\u7684\u94af\u5316 (palladation)\u8fc7\u7a0b\u3002\u5373\u7531\u4e8e\u53bb\u8d28\u5b50\u5316\u901f\u7387\u4e0e\u82b3\u57fa\u6b63\u79bb\u5b50\u00a0(arenium ion)\u7684\u5f62\u6210\u901f\u7387\u76f8\u5f53\uff0c\u56e0\u6b64\uff0c\u901a\u5e38\u60c5\u51b5\u4e0b\uff0c\u82b3\u9999\u4eb2\u7535\u53d6\u4ee3\u8fc7\u7a0b\u7684KIE\u6570\u503c\u8f83\u5c0f\uff0c\u751a\u81f3\u65e0\u6cd5\u89c2\u5bdf\u5230KIE\u7684\u5b58\u5728\u3002\u7531\u6b64\uff0c\u4f5c\u8005\u5047\u8bbe\uff0cC-2\u4f4d\u7684\u94af\u5316\u8fc7\u7a0b\uff0c\u4ecd\u7136\u53ef\u80fd\u901a\u8fc7SEAr\u673a\u7406\u8fdb\u884c\u3002 \u63a5\u4e0b\u6765\uff0c\u8be5\u5c0f\u7ec4\u901a\u8fc72-\u7898\u82ef\u915a\u73af\u5316\uff0c\u5f62\u6210\u4ea7\u72694\u7684\u53cd\u5e94\u8fc7\u7a0b\uff0c\u8fdb\u800c\u8bc1\u5b9e\u5177\u6709sp3\u78b3\u4e2d\u5fc3\u7684C-3-\u94af\u914d\u5408\u7269\u7684\u5b58\u5728\u3002\u5e76\u4e14\uff0c\u4ea7\u72694\u7684\u5f62\u6210\u8fc7\u7a0b\uff0c\u4e0e\u9884\u671f\u7684Heck\u578b\u6c27\u82b3\u57fa\u5316\u8fc7\u7a0b\u76f8\u4e00\u81f4\u3002\u5176\u4e2d\uff0c\u90bb\u8fd1\u7684\u7f9f\u57fa\u80fd\u591f\u8fdb\u4e00\u6b65\u53d6\u4ee3\u82ef\u5e76\u544b\u5583\u73af\u4e2d\u7684\u94af\u57fa\u56e2 (Scheme S1)\u3002\u76f8\u53cd\u5730\uff0c\u901a\u8fc7SEAr\u673a\u7406\u8fdb\u884c\u7684C-2\u94af\u5316\u8fc7\u7a0b\u4e2d\uff0c\u5728C-3\u4f4d\u7f6e\u80fd\u591f\u5f62\u6210\u76f8\u5e94\u7684\u78b3\u6b63\u79bb\u5b50\u4e2d\u5fc3 (Scheme S1)\u3002\u540c\u65f6\uff0c\u5728\u9178\u6027\u6761\u4ef6\u4e0b\uff0c2-\u7898\u82ef\u915a\u4e2d\u7684\u7f9f\u57fa\u5b98\u80fd\u56e2\u65e0\u6cd5\u4e0e\u78b3\u6b63\u79bb\u5b50\u4e2d\u5fc3\u8fdb\u884c\u6210\u952e\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u8003\u8651\u5230\uff0c\u540c\u6837\u53ef\u80fd\u5b58\u5728\u4e00\u79cd\u4e0e\u82b3\u57fa\u5316\u8fc7\u7a0b\u76f8\u4e92\u72ec\u7acb\u7684\u4e8c\u7ea7C-O\u952e\u7684\u5f62\u6210\u8fc7\u7a0b\u3002\u800c\u4e14\uff0c\u5373\u4f7f\u5728\u5e95\u7269\u5b8c\u5168\u8f6c\u5316\u4e4b\u524d\uff0c\u5c06\u53cd\u5e94\u8fc7\u7a0b\u505c\u6b62\uff0c\u540c\u6837\u65e0\u6cd5\u83b7\u5f97\u76f8\u5e94\u7684\u82b3\u57fa\u5316\u4ea7\u7269 (3h)\u3002\u5e76\u4e14\uff0c\u5bf9\u4e8e\u5176\u4ed6\u672a\u4fdd\u62a4\u7684\u9187\u5e95\u7269\uff0c\u5728\u4e0a\u8ff0\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u4e0b\u7684\u7a33\u5b9a\u6027\u7684\u76f8\u5173\u7814\u7a76\uff0c\u540c\u6837\u65e0\u6cd5\u8bc1\u5b9eSEAr\u8fc7\u7a0b\u5728C-O\u73af\u5316\u6b65\u9aa4\u4e4b\u524d\u8fdb\u884c\u3002\u540c\u65f6\uff0c\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u89c2\u5bdf\u4e0ePd\u50ac\u5316\u7684\u70ef\u57fa\u5316\u5408\u7269\u7684\u6c27\u82b3\u57fa\u5316\/C-H\u5b98\u80fd\u56e2\u5316\u8fc7\u7a0b\u4e00\u81f4\uff0c\u8fdb\u800c\u8868\u660e\u8fd9\u4e00\u5168\u65b0\u7684C-H\u82b3\u57fa\u5316\u8fc7\u7a0b\u4e0eHeck\u5316\u5b66\u4e4b\u95f4\u5177\u6709\u76f8\u4f3c\u6027\u3002\u800c\u4e14\uff0c\u901a\u8fc7\u4e0a\u8ff0\u5b9e\u9a8c\u89c2\u5bdf\uff0c\u80fd\u591f\u8fdb\u4e00\u6b65\u6392\u9664C-2\u4f4d\u82b3\u57fa\u5316\u8fc7\u7a0b\u901a\u8fc7SEAr\u673a\u7406\u8fdb\u884c\u7684\u53ef\u80fd\u6027\u3002 \u6700\u540e\uff0c\u7ed3\u5408\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u7814\u7a76\uff0c\u4f5c\u8005\u5047\u8bbe\u8fd9\u4e00\u5168\u65b0\u7684C-H\u82b3\u57fa\u5316\u8fc7\u7a0b\u901a\u8fc7Heck\u578b\u673a\u7406\u8def\u5f84\u8fdb\u884c (Scheme 5)\u3002\u9996\u5148\uff0c\u901a\u8fc7\u82b3\u57fa\u7898\u4e0ePd(0)\u4e4b\u95f4\u7684\u6c27\u5316\u52a0\u6210\u8fc7\u7a0b\uff0c\u5f62\u6210\u4e2d\u95f4\u4f53II\uff0c\u4e4b\u540e\uff0c\u4e2d\u95f4\u4f53II\u4e0e\u539f\u4f4d\u5f62\u6210\u7684\u7fa7\u9178\u94f6\u76d0\u4e4b\u95f4\u901a\u8fc7\u5364\u79bb\u5b50\u652b\u53d6 (halide abstraction)\u6b65\u9aa4\uff0c\u5f62\u6210\u5177\u6709\u66f4\u9ad8\u53cd\u5e94\u6d3b\u6027\u7684\u94af\u91d1\u5c5e\u4e2d\u5fc3\uff0c\u540c\u65f6\uff0c\u901a\u8fc7\u94af\u91d1\u5c5e\u4e2d\u5fc3\u4e2d\u65b0\u5f15\u5165\u7684\u7fa7\u57fa\u8d1f\u79bb\u5b50\u914d\u4f53\u7684\u8fdb\u4e00\u6b65\u89e3\u79bb\uff0c\u5f62\u6210\u94af\u9633\u79bb\u5b50\u914d\u5408\u7269\u00a0III\u3002\u63a5\u4e0b\u6765\uff0c1a\u4e0e\u94af\u9633\u79bb\u5b50\u914d\u5408\u7269\u00a0III\u4e4b\u95f4\u7ecf\u5386\u94af\u78b3\u5316 (carbopalladation)\u6b65\u9aa4\uff0c\u5f62\u6210\u4e2d\u95f4\u4f53IV\uff0c\u5e76\u8fdb\u4e00\u6b65\u901a\u8fc7\u78b1\u8f85\u52a9\u7684anti-\u03b2-\u6d88\u9664\u6b65\u9aa4\uff0c\u8fdb\u800c\u83b7\u5f97\u76ee\u6807\u4ea7\u72693\uff0c\u540c\u65f6\uff0c\u4f7fPd(0)\u50ac\u5316\u5242\u518d\u751f\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u5047\u8bbe\uff0c\u5364\u79bb\u5b50\u652b\u53d6\u4ee5\u53ca\u540e\u7eed\u7684\u914d\u4f53\u89e3\u79bb\u8fc7\u7a0b\uff0c\u662f\u4e0a\u8ff0C-H\u82b3\u57fa\u5316\u53cd\u5e94\u8fc7\u7a0b\u80fd\u591f\u5728\u5ba4\u6e29\u6761\u4ef6\u4e0b\u987a\u5229\u8fdb\u884c\u7684\u5173\u952e\u3002\u6b64\u5916\uff0c\u9664\u901a\u8fc7\u6c22\u952e\u4f5c\u7528[8]\uff0c\u4f7f\u6d3b\u6027\u94af\u914d\u5408\u7269\u7a33\u5b9a\u5316\u4e4b\u5916\uff0cHFIP\u540c\u6837\u53ef\u80fd\u4e0e\u7fa7\u9178\u94f6\u4e4b\u95f4\u8fdb\u884c\u76f8\u5e94\u7684\u9178\u78b1\u4ea4\u6362\u8fc7\u7a0b[9]\u3002 \u603b\u7ed3 Washington\u5927\u5b66\u7684C. K. Luscombe\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u82ef\u5e76\u544b\u5583\u884d\u751f\u7269\u7684\u533a\u57df\u9009\u62e9\u6027C-2\u82b3\u57fa\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002\u5e76\u4e14\uff0c\u8fd9\u4e00\u5168\u65b0\u7684C-H\u82b3\u57fa\u5316\u7b56\u7565\u5177\u6709\u53cd\u5e94\u6761\u4ef6\u6e29\u548c\u4ee5\u53ca\u6781\u4e3a\u4f18\u826f\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u7b49\u4f18\u52bf\u3002\u540c\u65f6\uff0c\u4f5c\u8005\u8bbe\u60f3\uff0c\u4e0a\u8ff0\u7684C-H\u82b3\u57fa\u5316\u8fc7\u7a0b\u901a\u8fc7Heck\u578b\u82b3\u57fa\u5316\u673a\u7406\u8fdb\u884c\u3002 \u53c2\u8003\u6587\u732e [1]\u00a0(a) S. C. Yin, Q. Zhou, X. Y. Zhao, L. X. Shao, J. Org.\u00a0Chem.\u00a02015, 80, 891.\u00a0doi:\u00a010.1021\/acs.joc.5b01544. (b) J. Cao, Z. L. Chen, S. M. Li, G. F. Zhu, Y. Y. Yang, C. Wang,\u00a0W. Z. Chen, J. T. Wang, […]","protected":false},"author":26,"featured_media":40265,"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":[1271],"tags":[3620,392,3618,3619],"jetpack_publicize_connections":[],"jetpack_featured_media_url":"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/10\/1-1.png","jetpack_shortlink":"https:\/\/wp.me\/p96op1-atA","jetpack_sharing_enabled":true,"_links":{"self":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/40274"}],"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\/26"}],"replies":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/comments?post=40274"}],"version-history":[{"count":2,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/40274\/revisions"}],"predecessor-version":[{"id":40278,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/40274\/revisions\/40278"}],"wp:featuredmedia":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media\/40265"}],"wp:attachment":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media?parent=40274"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/categories?post=40274"},{"taxonomy":"post_tag","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/tags?post=40274"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}