{"id":30032,"date":"2020-03-09T08:10:23","date_gmt":"2020-03-09T00:10:23","guid":{"rendered":"\/\/www.gsbet888.com\/?p=30032"},"modified":"2020-03-05T23:11:25","modified_gmt":"2020-03-05T15:11:25","slug":"ario2cr2%e8%af%95%e5%89%82%e7%9b%b4%e6%8e%a5%e4%bf%83%e8%bf%9b%e7%83%af%e9%85%aec-h%e7%9a%84%ce%b1-%e8%8a%b3%e5%9f%ba%e5%8c%96","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2020\/03\/ario2cr2%e8%af%95%e5%89%82%e7%9b%b4%e6%8e%a5%e4%bf%83%e8%bf%9b%e7%83%af%e9%85%aec-h%e7%9a%84%ce%b1-%e8%8a%b3%e5%9f%ba%e5%8c%96.html","title":{"rendered":"ArI(O2CR)2\u8bd5\u5242\u76f4\u63a5\u4fc3\u8fdb\u70ef\u916eC-H\u7684\u03b1-\u82b3\u57fa\u5316"},"content":{"rendered":"

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

\u5bfc\u8bfb<\/h4>\n

\u03b1<\/em>,\u03b2<\/em>-\u4e0d\u9971\u548c\u916e\u7684\u03b1<\/em>-\u82b3\u57fa\u5316\u53cd\u5e94\u4f5c\u4e3a\u5408\u6210\u4e2d\u5e38\u7528\u7684\u624b\u6bb5\u4e4b\u4e00\uff0c\u901a\u5e38\u4ee5\u03b1<\/em>-\u5364\u4ee3\u70ef\u7684\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\u6765\u5b9e\u73b0\uff0c\u4f46\u5e38\u5e38\u9700\u8981\u5e95\u7269\u7684\u9884\u5b98\u80fd\u56e2\u5316\u548c\u4f7f\u7528\u6602\u8d35\u7684\u50ac\u5316\u5242\u3002\u800c\u70ef\u916e\u76f4\u63a5C-H\u7684\u03b1<\/em>-\u82b3\u57fa\u5316\u5219\u4f53\u73b0\u4e86\u539f\u5b50\u548c\u6b65\u9aa4\u7ecf\u6d4e\u6027\u7684\u7279\u70b9\uff0c\u4f46\u5f88\u5c11\u6709\u6587\u732e\u62a5\u9053\u3002\u8fd1\u65e5\uff0c\u5929\u666e\u5927\u5b66Wengryniuk\u6559\u6388\u8bfe\u9898\u7ec4\u5728JACS\u53d1\u8868\u8bba\u6587\uff0c\u5728\u65e0\u91d1\u5c5e\u50ac\u5316\u5242\u65f6\uff0c\u901a\u8fc7\u9ad8\u4ef7\u82b3\u57fa\u7898\u8bd5\u5242\u4f5c\u4e3a\u5e95\u7269\uff0c\u5b9e\u73b0\u70ef\u916e\u7684\u76f4\u63a5C-H\u82b3\u57fa\u5316\u53cd\u5e94\u3002\u8be5\u53cd\u5e94\u901a\u8fc7\u539f\u4f4d\u4ea7\u751f\u7684\u03b2<\/em>-\u5421\u5576\u57fa\u7532\u7845\u70f7\u57fa\u70ef\u9187\u919a\u4e2d\u95f4\u4f537<\/strong>\uff0c\u7ecf\u8fd8\u539f\u6027\u7898\u9393-Claisen\u91cd\u6392\u83b7\u5f97\u03b1<\/em>-\u82b3\u57fa\u4ea7\u7269\u3002\u4ea7\u7269\u4e2d\u7684\u82b3\u57fa\u6765\u81eaArI(O2<\/sub>CCF3<\/sub>)2<\/sub>\u8bd5\u5242\uff0c\u540c\u65f6\u8be5\u53cd\u5e94\u5177\u6709\u8f83\u597d\u7684\u517c\u5bb9\u6027\uff0c\u53ef\u5408\u6210\u591a\u79cd\u7898\u4ee3\u82b3\u57fa\u884d\u751f\u7269\u3002\u673a\u7406\u7814\u7a76\u8868\u660e\uff0c\u4e2d\u95f4\u4f537<\/strong>\u4f5c\u4e3a\u53cd\u5e94\u6210\u529f\u7684\u5173\u952e\uff0c\u540c\u65f6\u03b2<\/em>-\u5421\u5576\u7ed3\u6784\u5bf9\u4e8e\u6240\u9700C-C\u952e\u7684\u5f62\u6210\u81f3\u5173\u91cd\u8981\u3002<\/p>\n

Direct C\u2013H \u03b1-Arylation of Enones with ArI(O2<\/sub>CR)2<\/sub> Reagents<\/p>\n

Felipe Cesar Sousa e SilvaNguyen T. VanSarah E. Wengryniuk*<\/p>\n

J. Am. Chem. Soc.<\/em> 2020<\/strong>, 142<\/em>, 1, 64-69. \u00a0DOI\uff1a10.1021\/jacs.9b11282<\/a><\/p><\/blockquote>\n

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

\u6b63\u6587<\/h4>\n

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

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

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

\u4f7f\u7528\u73af\u5df1\u70ef\u916e\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\u65f6\uff0c\u4f7f\u7528\u5421\u5576\u4f5c\u4e3a\u5916\u6e90\u6027\u4eb2\u6838\u8bd5\u5242\u65f6\uff0c\u4fc3\u4f7f\u5421\u5576\u76f8\u8fde\u7684N<\/em>-HVI [PhI(Py)2<\/sub>](OTf)2<\/sub>\u53cd\u5e94\u83b7\u5f97\u6536\u738723\uff05\u7684\u03b1<\/em>-\u7898\u4ee3\u82b3\u57fa\u70ef\u916e12<\/strong>\uff08Scheme 2B \uff09\u3002\u9057\u61be\u7684\u662f\uff0c\u5728\u7b5b\u9009\u4e86N<\/em>-HVI\u3001\u5176\u4ed6I(III)\u8bd5\u5242\u3001\u03b2<\/em>-\u4eb2\u6838\u8bd5\u5242\u548c\u53cd\u5e94\u6761\u4ef6\u65f6\uff0c\u5747\u65e0\u6cd5\u4f7f\u82b3\u57fa\u5316\u53cd\u5e94\u4ea7\u7387\u63d0\u9ad8\u3002\u4f5c\u8005\u63a8\u6d4b\uff0c\u53ef\u80fd\u662f\u7531\u4e8eI(III)\u8bd5\u5242\u4e0e\u4eb2\u6838\u8bd5\u5242\u4e4b\u95f4\u7ade\u4e89\u6027\u5bfc\u81f4\u8f83\u5dee\u7684\u7ed3\u679c\uff08\u5982\u914d\u4f53\u4ea4\u6362\u3001\u6c27\u5316\u964d\u89e3\u3001\u914d\u4f53\u5076\u8054\u7b49\uff09\u3002\u4e3a\u4e86\u89e3\u51b3\u8fd9\u4e2a\u95ee\u9898\uff0c\u4f5c\u8005\u63d0\u51fa\u4e86\u4e00\u6b65\u6cd5\u7684\u82b3\u57fa\u5316\u8fc7\u7a0b\uff0c\u5176\u4e2d\u5c06ArIX2<\/sub>\u52a0\u5165\u5230\u539f\u4f4d\u5f62\u6210\u7684\u70ef\u9178\u916f\u4e2d\u3002\u6b64\u5916\uff0c\u6839\u636eKim\u62a5\u9053\u6587\u732e\u7684\u603b\u7ed3\uff0c\u4f5c\u8005\u4f7f\u7528TMSOTf\u548c\u5421\u5576\u4f5c\u4e3a\u53cd\u5e94\u6761\u4ef6\uff0c\u901a\u8fc71<\/sup>H NMR\u5206\u6790\u4ece\u800c\u8bc1\u660e\u4e86\u03b2<\/em>-\u5421\u5576\u57fa\u7532\u7845\u70f7\u57fa\u70ef\u9187\u919a13<\/strong>\u7684\u5b8c\u5168\u8f6c\u5316\uff08Scheme 2C\uff09\u3002<\/p>\n

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

\u9996\u5148\uff0c\u4f5c\u8005\u4ee511<\/strong>\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u5728\u4e0a\u8ff0\u6761\u4ef6\u4e0b\u83b7\u5f97\u03b2<\/em>-\u5421\u5576\u57fa\u7532\u7845\u70f7\u57fa\u70ef\u9187\u919a13<\/strong>\u540e\uff0c\u5bf9I(III)\u8bd5\u5242\u4e0e\u6dfb\u52a0\u5242\u8fdb\u884c\u4e86\u7b5b\u9009\uff08Table 1\uff09\u3002\u5f53\u4ee5[PhI(Py)2<\/sub>](OTf)2<\/sub>\u4f5c\u4e3a\u82b3\u57fa\u7898\u8bd5\u5242\u65f6\uff0c\u52a0\u70ed\u81f380\u2103\u53cd\u5e9418 h\uff0c\u83b7\u5f9730%\u6536\u7387\u7684\u03b1<\/em>-\u82b3\u57fa\u5316\u4ea7\u726912<\/strong>\uff08entry 1\uff09\u3002\u800c\u4f7f\u7528PhI(OTFA)2<\/sub>\u8bd5\u5242\u65f6\uff0c\u53cd\u5e9412h\u53ef\u5c06\u6536\u7387\u63d0\u9ad8\u81f346\uff05\uff08entry 2\uff09\u3002\u6709\u8da3\u7684\u662f\uff0c\u5e76\u6ca1\u6709\u53d1\u73b0\u03b1<\/em>-\u6c27\u5316\u526f\u4ea7\u7269\uff0c\u901a\u8fc7NMR\u5206\u6790\u53ef\u77e5\uff0c\u53cd\u5e94\u4e2d\u5b58\u5728\u82b3\u57fa\u5316\u5421\u5576\u9393\u76d0\u4e2d\u95f4\u4f5314<\/strong>\uff08\u5206\u79bb\u4e0d\u7a33\u5b9a\uff09\uff0c\u540c\u65f6\u5728\u4f4e\u6e29\u4e0b\u03b1<\/em>-\u82b3\u57fa\u5316\u8fc5\u901f\u53d1\u751f\uff08<10min\uff09\uff0c\u800c14<\/strong>\u81f312<\/strong>\u7684\u8f6c\u5316\u5219\u4e3a\u7f13\u6162\u8fc7\u7a0b\u3002\u6839\u636e\u8fd9\u4e00\u53d1\u73b0\uff0c\u4f5c\u8005\u5bf9\u5404\u79cd\u6dfb\u52a0\u5242\u8fdb\u884c\u4e86\u7814\u7a76\uff0c\u4ee5\u52a0\u5feb\u03b2<\/em>-\u5421\u5576\u76d0\u7684\u6d88\u9664\u3002\u572840\u2103\u65f6\uff0c\u6dfb\u52a0NEt3<\/sub>\u53ef\u4f7f\u6536\u7387\u663e\u7740\u63d0\u9ad8\u81f383\uff05\uff08entry 3\uff09\uff0c\u800c\u4f7f\u7528\u9178\u6027\u4e8c\u6c27\u5316\u7845\/ MeOH\u53ef\u8fdb\u4e00\u6b65\u5c06\u6536\u7387\u63d0\u81f390\uff05\uff08entry 4\uff09\u3002\u800c\u5c06\u82b3\u57fa\u7898\u8bd5\u5242\u6539\u4e3aPhI(OAc)2<\/sub>\u65f6\uff0c\u65e0\u8bba\u52a0\u5165\u78b1\u6027\u548c\u9178\u6027\u6dfb\u52a0\u5242\u5747\u4f7f\u6536\u7387\u6709\u6240\u4e0b\u964d\uff08entries 5-6\uff09\u3002\u5982\u679c\u4f7f\u7528\u5176\u5b83\u4e8c\u82b3\u57fa\u7898\u9393\u76d0\u8fdb\u884c\u82b3\u57fa\u5316\u65f6\uff08entries 7-8\uff09\uff0c\u5747\u672a\u53cd\u5e94\uff0c\u8fdb\u4e00\u6b65\u8bf4\u660e\u4e86\u03b2<\/em>-\u5421\u5576\u9393\u7c7b\u5316\u5408\u7269\u5bf9\u8be5\u53cd\u5e94\u7684\u91cd\u8981\u6027\u3002<\/p>\n

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

\u5728\u83b7\u5f97\u4e0a\u8ff0\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u540e\uff0c\u4f5c\u8005\u5f00\u59cb\u5bf9\u5e95\u7269\u70ef\u916e\u4e0e\u8fdb\u884c\u4e86\u6269\u5c55\uff08Table 2\uff09\u3002\u9996\u5148\uff0c\u4f5c\u8005\u5bf9\u82b3\u57fa\u7898\u8bd5\u5242\u8fdb\u884c\u4e86\u6269\u5c55\uff0c\u82b3\u57fa\u7898\u5316\u7269\u4e0d\u53d7\u5b9a\u4f4d\u6548\u5e94\u5f71\u54cd\uff0c\u5747\u53ef\u83b7\u5f97\u76f8\u5e94\u7684\u03b1<\/em>-(2-\u7898\u4ee3\u82b3\u57fa)\u70ef\u916e15<\/strong>–19<\/strong>\u3002\u800c\u5bf9\u7535\u5b50\u6548\u5e94\u7684\u7814\u7a76\u8868\u660e\uff0815<\/strong>–24<\/strong>\uff09\uff0c\u5438\u7535\u5b50\u57fa\u5e38\u5e38\u5bfc\u81f4\u8f83\u4f4e\u7684\u6536\u7387\uff0c\u5982-NO2<\/sub>\u3001-CN\u7b49\u3002\u540c\u65f6\uff0c\u4e00\u4e9b\u5728\u90bb\u4f4d\u3001\u95f4\u4f4d\u548c\u5bf9\u4f4d\u542b\u6709\u5364\u7d20\u7684\u5e95\u7269\u4e5f\u88ab\u7814\u7a76\uff0c\u56e0\u4e3a\u8fd9\u4e9b\u4ea7\u7269\u53ef\u8fdb\u884c\u591a\u79cd\u540e\u671f\u4fee\u9970\uff0c\u5e76\u4e14\u4e5f\u4e3a\u4f20\u7edf\u7684\u91d1\u5c5e\u50ac\u5316\u5076\u8054\u53cd\u5e94\u63d0\u4f9b\u4e86\u9009\u62e9\u6027\u5076\u8054\u5e95\u7269\u3002\u867d\u7136\u5747\u53ef\u83b7\u5f97\u76f8\u5e94\u7684\u82b3\u57fa\u5316\u4ea7\u7269\uff0825<\/strong>–33<\/strong>\uff09\uff0c\u4f46\u6536\u7387\u548c\u53d6\u4ee3\u4f4d\u7f6e\u4e4b\u95f4\u51fa\u73b0\u4e86\u660e\u663e\u7684\u8d8b\u52bf\uff08\u5bf9>\u95f4\u226b\u90bb\uff09\u3002\u540c\u65f6\uff0c\u591a\u53d6\u4ee3\u7684\u82b3\u70c3\uff0834<\/strong>\u300135<\/strong>\uff09\uff0c\u5bcc\u7535\u5b50\u7684\u6742\u82b3\u65cf\u5316\u5408\u7269\uff0836<\/strong>\u300137<\/strong>\uff09\uff0c\u4e5f\u540c\u6837\u5b9e\u73b0\u4e86\u82b3\u57fa\u5316\u53cd\u5e94\u3002\u800c\u5bf9\u70ef\u916e\u5e95\u7269\u6269\u5c55\u65f6\uff0c\u73af\u620a\u70ef\u916e\uff0838<\/strong>\uff09\u548c\u65e0\u73af\u5df4\u8c46\u919b\uff0840<\/strong>\uff09\u7684\u82b3\u57fa\u5316\u6536\u7387\u8f83\u9ad8\uff0c\u800c\u4f7f\u7528\u73af\u5e9a\u70ef\u916e\uff0839<\/strong>\uff09\u4ec5\u83b7\u5f9712\uff05\u7684\u6536\u7387\u3002<\/p>\n

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

\u968f\u540e\uff0c\u4f5c\u8005\u5f00\u59cb\u5bf9\u4ea7\u7269\u03b1<\/em>-(2-\u7898\u82b3\u57fa)\u70ef\u916e\u8fdb\u884c\u4e86\u540e\u671f\u4fee\u9970\uff0c\u53ef\u6709\u6548\u7684\u6784\u5efa\u591a\u73af\u6742\u82b3\u70c3\uff08Scheme 3\uff09\u3002\u5229\u7528\u7fb0\u57fa\u6c27\u4e0e\u7898\u7684\u5076\u8054\u53ef\u83b7\u5f97\u4f18\u5f02\u6536\u7387\u7684\u82ef\u5e76\u544b\u5583\u884d\u751f\u7269\uff0841<\/strong>–44<\/strong>\uff09\u3002 \u540c\u65f6\u5432\u54da\u7c7b\u9aa8\u67b6\u5df2\u5e7f\u6cdb\u5e94\u7528\u4e8e\u5929\u7136\u4ea7\u7269\u7684\u5408\u6210\u4e2d\uff0c\u800c\u4ee5\u785d\u57fa\u884d\u751f\u726945<\/strong>\u4f5c\u4e3a\u5e95\u7269\u65f6\uff0c\u53ef\u901a\u8fc7\u76f8\u5173\u65b9\u6cd5\u5408\u6210\u591a\u79cd\u5432\u54da\u7c7b\u884d\u751f\u7269\u3002<\/p>\n

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

\u4e3a\u4e86\u8fdb\u4e00\u6b65\u4e86\u89e3\u53cd\u5e94\u673a\u7406\uff0c\u4f5c\u8005\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u5bf9\u7167\u5b9e\u9a8c\uff08Scheme 4\uff09\u3002\u5728\u4f7f\u7528\u03b2<\/em>-\u5421\u5576\u76d0\u4e2d\u95f4\u4f5313<\/strong>\u65f6\uff0c\u5728\u5f62\u6210\u7684\u82b3\u57fa\u5316\u8fc7\u7a0b\u4e2d\u5e76\u6ca1\u6709\u89c2\u5bdf\u5230\u03b1<\/em>-\u6c27\u5316\u526f\u4ea7\u7269\uff08Scheme 4A\uff09\u3002\u6b64\u5916\uff0c\u5c06\u03b2<\/em>-\u672a\u53d6\u4ee3\u7684\u7532\u7845\u70f7\u57fa\u70ef\u9187\u919a45<\/strong>\u7528PhI(OCOCF3<\/sub>)2<\/sub>\u5904\u7406\uff0c\u83b7\u5f97\u7b49\u91cf\u7684\u03b1<\/em>-\u6c27\u5316\u4ea7\u726947<\/strong>\uff0c\u8bf4\u660e\u5728\u6ca1\u6709\u4efb\u4f55\u70ef\u9187\u5316\u7269\u65f6\u4ec5\u83b7\u5f97\u03b1<\/em>-\u6c27\u5316\u7269\uff08Scheme 4B\uff09\u3002\u63a5\u4e0b\u6765\uff0c\u4e3a\u4e86\u6d88\u9664\u7535\u5b50\u6548\u5e94\u7684\u5f71\u54cd\uff0c\u4ee5\u03b2<\/em>-\u82ef\u57fa\u7532\u7845\u70f7\u57fa\u70ef\u9187\u919a\u4e3a\u5e95\u7269\u5728\u4e0a\u8ff0\u6807\u51c6\u6761\u4ef6\u53cd\u5e94\uff08Scheme 4B\uff09\u3002\u6709\u8da3\u7684\u662f\uff0c\u83b7\u5f97\u4ea7\u7269\u964d\u89e3\u7684\u6df7\u5408\u7269\uff0c\u540c\u65f6\u65e0\u03b1<\/em>-\u6c27\u5316\u6216\u03b1<\/em>-\u82b3\u57fa\u5316\u4ea7\u7269\u3002\u8be5\u7ed3\u679c\u8868\u660e\uff0c\u5355\u72ec\u7684\u82ef\u57fa\u4e0d\u8db3\u4ee5\u5b9e\u73b0\u6709\u6548\u7684\u03b1<\/em>-\u82b3\u57fa\u5316\uff0c\u4f46\u786e\u5b9e\u8d77\u5230\u6291\u5236\u5206\u5b50\u95f4\u7684\u4f5c\u7528\u3002\u7efc\u4e0a\u6240\u8ff0\uff0c\u03b2<\/em>-\u5421\u5576\u57fa\u4e2d\u95f4\u4f53\u53ef\u80fd\u901a\u8fc7\u7a7a\u95f4\u4e0e\u7535\u5b50\u6548\u5e94\u7684\u76f8\u4e92\u4f5c\u7528\u6765\u8c03\u8282\u53cd\u5e94\u8fc7\u7a0b\uff08Scheme 4 inset\uff09\u3002<\/p>\n

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

\u603b\u7ed3<\/h4>\n

\u672c\u6587\u4e3b\u8981\u4ecb\u7ecd\u4e86\u4e00\u79cd\u901a\u8fc7ArI(O2<\/sub>CCF3<\/sub>)2<\/sub>\u8bd5\u5242\u76f4\u63a5\u8fdb\u884c\u70ef\u916eC-H\u7684\u03b1<\/em>-\u82b3\u57fa\u5316\u53cd\u5e94\u3002\u8be5\u53cd\u5e94\u901a\u8fc7\u539f\u4f4d\u4ea7\u751f\u03b2<\/em>-\u5421\u5576\u57fa\u7532\u7845\u70f7\u57fa\u70ef\u9187\u919a\u4e2d\u95f4\u4f537<\/strong>\uff0c\u7136\u540e\u8fdb\u884c\u8fd8\u539f\u6027[3,3]\u91cd\u6392\uff0c\u83b7\u5f97\u591a\u79cd\u03b1<\/em>-\u82b3\u57fa\u5316\u884d\u751f\u7269\uff0c\u540c\u65f6\u4f5c\u4e3a\u7b2c\u4e00\u4e2a\u7898\u9393-\u514b\u83b1\u68ee\u91cd\u6392\u7684\u4f8b\u5b50\u3002\u901a\u8fc7\u5c06\u03b1<\/em>-(2-\u7898\u82b3\u57fa)\u70ef\u916e\u540e\u671f\u4fee\u9970\uff0c\u5408\u6210\u591a\u79cd\u5177\u6709\u4ef7\u503c\u7684\u6742\u73af\u9aa8\u67b6\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u8be5\u65b9\u6cd5\u7684\u5b9e\u7528\u6027\u3002\u673a\u7406\u7814\u7a76\u8868\u660e\uff0c\u03b2<\/em>-\u5421\u5576\u57fa\u4e2d\u95f4\u4f53\u7684\u7a7a\u95f4\u4e0e\u7535\u5b50\u6548\u5e94\u5bf9\u4e8e\u53cd\u5e94\u81f3\u5173\u91cd\u8981\u3002<\/p>\n

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