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\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749<\/p>\n
\u8fd1\u65e5\uff0c\u4f0a\u5229\u8bfa\u4f0a\u5927\u5b66Mankad Neal\u6559\u6388\u8bfe\u9898\u7ec4\u5728JACS<\/em>\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e86Cu\u50ac\u5316\u4e0b\uff0c\u5b9e\u73b0\u672a\u6d3b\u5316\u70f7\u57fa\u5364\u5316\u7269\u7684\u7fb0\u57fa\u7845\u70f7\u5316\u53cd\u5e94\uff0c\u9ad8\u6548\u5730\u5408\u6210\u4e86\u70f7\u57fa\u53d6\u4ee3\u7684\u9170\u57fa\u7845\u70f7\u884d\u751f\u7269\u3002\u5728\u6e29\u548c\u7684\u53cd\u5e94\u6761\u4ef6\u4e0b\u53ef\u4ee5\u8010\u53d7\u591a\u79cd\u5b98\u80fd\u56e2\uff0c\u4f2f\u3001\u4ef2\u548c\u53d4\u70f7\u57fa\u5364\u5316\u7269\u5747\u53ef\u9002\u7528\u3002\u6b64\u5916\uff0c\u8be5\u65b9\u6cd5\u4e0d\u4ec5\u5408\u6210\u4e0d\u540c\u7532\u7845\u70f7\u57fa\u7684\u9170\u57fa\u7845\u70f7\u884d\u751f\u7269\uff0c\u540c\u65f6\u53ef\u5c06\u4ea7\u7269\u8fd8\u539f\u4e3a\u76f8\u5e94\u7684\u03b1<\/em>-\u7f9f\u57fa\u7845\u70f7\u884d\u751f\u7269\u3002\u673a\u7406\u7814\u7a76\u8868\u660e\uff0c\u7532\u7845\u70f7\u57fa\u94dc\u4e2d\u95f4\u4f53\u901a\u8fc7\u5355\u7535\u5b50\u8f6c\u79fb\u6d3b\u5316\u70f7\u57fa\u5364\uff0c\u5f62\u6210\u70f7\u57fa\u81ea\u7531\u57fa\u4e2d\u95f4\u4f53\uff0c\u8fdb\u800c\u8fdb\u884c\u7fb0\u57fa\u7845\u70f7\u5316\u53cd\u5e94\u3002<\/p>\n Cu-Catalyzed Carbonylative Silylation of Alkyl Halides: Efficient Access to Acylsilanes<\/p>\n Li-Jie Cheng, Neal P. Mankad*<\/p>\n J. Am. Chem. Soc.<\/em> 2020<\/strong>, 142<\/em>, 1, 80-84. DOI\uff1a10.1021\/jacs.9b12043<\/a><\/p><\/blockquote>\n \u6709\u673a\u7845\u70f7\u5316\u5408\u7269\u5e7f\u6cdb\u5e94\u7528\u4e8e\u6709\u673a\u5408\u6210\u548c\u6750\u6599\u79d1\u5b66\u4e2d\uff0c\u542b\u6709\u9170\u57fa\u7845\u70f7\u7684\u7ed3\u6784\u5355\u5143\u4f5c\u4e3a\u5178\u578b\u4ee3\u8868\uff0cBrook\u91cd\u6392\u662f\u5236\u5907\u6b64\u7c7b\u9aa8\u67b6\u7684\u5e38\u7528\u65b9\u6cd5\u3002\u7136\u800c\uff0c\u5927\u591a\u6570\u5df2\u62a5\u9053\u6587\u732e\u4e2d\u5b58\u5728\u4e00\u4e9b\u4e0d\u8db3\uff0c\u5982\u9700\u591a\u6b65\u5236\u5907\u3001\u5e95\u7269\u8303\u56f4\u7a84\u7b49\u3002Brook\u548cCorey\u62a5\u9053\u7684\u7ecf\u5178\u5408\u6210\u8def\u7ebf\u4e2d\uff0c\u4ece\u919b\u7c7b\u5e95\u7269\u4e2d\u5408\u6210\u9170\u57fa\u7845\u70f7\u884d\u751f\u7269\uff0c\u4f46\u9700\u8981\u7e41\u7410\u7684\u4fdd\u62a4\/\u8131\u4fdd\u62a4\u8fc7\u7a0b\uff08Scheme 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\u5728\u83b7\u5f97\u4e0a\u8ff0\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u540e\uff0c\u4f5c\u8005\u5f00\u59cb\u5bf9\u5e95\u7269\u8fdb\u884c\u4e86\u6269\u5c55(Table 2)\u3002\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0c\u70f7\u57fa\u7898\u5316\u7269\u672b\u7aef\u542b\u6709\u82ef\u57fa\uff082b<\/strong>\uff09\u3001\u82c4\u57fa\u919a\uff082c<\/strong>\uff09\u3001\u6c2f\u70f7\u57fa\uff082d<\/strong>\uff09\u3001\u672b\u7aef\u70ef\u70c3\uff082n<\/strong>\uff09\u7b49\uff0c\u5747\u83b7\u5f97\u8f83\u597d\u7684\u7ed3\u679c\u3002\u800c\u542b\u6709\u6742\u73af\u7684\u5e95\u7269\u4e5f\u80fd\u591f\u4e0e\u4f53\u7cfb\u517c\u5bb9\uff0c\u5982\u544b\u5583\uff082e<\/strong>\uff09\u3001\u567b\u5429\uff082f<\/strong>\uff09\u3001\u5432\u54da\u57fa\uff082g<\/strong>\uff09\u7b49\u3002\u672b\u7aef\u82ef\u57fa\uff082h<\/strong>–2l<\/strong>\uff09\u542b\u6709\u4e09\u6c1f\u7532\u57fa\u3001\u916f\u57fa\u3001\u6c30\u57fa\u3001\u6c2f\u57fa\u3001\u6eb4\u57fa\u53d6\u4ee3\u65f6\uff0c\u4e5f\u53ef\u83b7\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u7269\uff0c\u4f46\u7898\u53d6\u4ee3\u7684\u5e95\u7269\uff082m<\/strong>\uff09\u5b58\u5728\u4e00\u5b9a\u7684\u526f\u53cd\u5e94\u3002\u968f\u540e\uff0c\u4f5c\u8005\u5c06\u4f2f\u70f7\u57fa\u7898\u6269\u5927\u5230\u4ef2\u70f7\u57fa\u7898\uff0c\u5e95\u7269\u4ef2\u70f7\u57fa\u7898\uff082o<\/strong>–2r<\/strong>\uff09\u4e0d\u53d7\u4f4d\u963b\u5f71\u54cd\uff0c\u540c\u65f6\u73af\u70f7\u57fa\u7898\uff082s<\/strong>\u30012t<\/strong>\uff09\u4e5f\u4e0e\u4f53\u7cfb\u517c\u5bb9\u3002\u968f\u540e\uff0c\u53d4\u70f7\u57fa\u4eb2\u7535\u4f53\uff082u<\/strong>–2y<\/strong>\uff09\u4e5f\u83b7\u5f97\u4e86\u4ee4\u4eba\u6ee1\u610f\u7684\u7ed3\u679c\uff0c\u540c\u65f6\u5177\u6709\u66f4\u9ad8\u7684\u6536\u7387\u3002<\/p>\n \u4e3a\u4e86\u9a8c\u8bc1\u8be5\u65b9\u6cd5\u7684\u9002\u7528\u6027\uff0c\u4f5c\u8005\u8fdb\u884c\u4e86\u5982\u4e0b\u5b9e\u9a8c\uff08Scheme 2\uff09\u3002\u9996\u5148\uff0c\u514b\u7ea7\u5b9e\u9a8c\u540c\u6837\u4ee5\u9ad8\u6536\u7387\u83b7\u5f97\u4e86\u9884\u671f\u7684\u9170\u57fa\u7845\u70f7\u4ea7\u72692a<\/strong>\uff08Scheme 2a\uff09\u3002\u6b64\u5916\uff0c\u8be5\u65b9\u6848\u53ef\u5bf9\u5929\u7136\u4ea7\u7269\u6216\u836f\u7269\u8fdb\u884c\u540e\u671f\u7684\u4fee\u9970\u3002\u5982\u96cc\u916e\u884d\u751f\u72694<\/strong>\uff0c\u5728\u4e0a\u8ff0\u6807\u51c6\u6761\u4ef6\u4e0b\uff0c\u4ee5\u4f18\u5f02\u7684\u4ea7\u7387\u83b7\u5f97\u9170\u57fa\u7845\u70f75\uff08Scheme 2b\uff09\u3002\u6b64\u5916\uff0c\u9664\u4e86PhMe2<\/sub>Si-Bpin\u4f5c\u4e3a\u7532\u7845\u70f7\u57fa\u6765\u6e90\u5916\uff0c\u6d3b\u6027\u8f83\u4f4e\u7684Et3<\/sub>Si-Bpin\uff08\u9ad8\u6e29\u4e0b\uff09\u4e5f\u53ef\u4f5c\u4e3a\u5076\u8054\u5e95\u7269\uff08Scheme 2c\uff09\u3002\u5982\u679c\u5728\u53cd\u5e94\u5b8c\u6210\u4e4b\u540e\uff0c\u5411\u53cd\u5e94\u6df7\u5408\u7269\u4e2d\u52a0\u5165\u6c22\u7845\u70f7\uff0c\u53ef\u8fdb\u4e00\u6b65\u8fd8\u539f\u9170\u57fa\u7845\u70f7\uff08Scheme 2d\uff09\u3002\u56e0\u6b64\uff0c\u8be5\u65b9\u6848\u4e5f\u4f5c\u4e3a\u5408\u6210\u03b1<\/em>-\u7f9f\u57fa\u7845\u70f7\uff08\u70f7\u57fa\u5364\u5316\u7269\u4f5c\u4e3a\u5e95\u7269\uff09\u7684\u6709\u6548\u65b9\u6cd5\u3002<\/p>\n \u4e3a\u4e86\u8fdb\u4e00\u6b65\u9a8c\u8bc1\u673a\u7406\u7684\u6b63\u786e\u6027\uff0c\u4f5c\u8005\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u5bf9\u7167\u5b9e\u9a8c\uff08Scheme 3\uff09\u3002\u5f53\u5c06TEMPO\u52a0\u5165\u53cd\u5e94\u4e2d\u65f6\uff0c\u672a\u83b7\u5f97\u76ee\u6807\u4ea7\u7269\uff0c\u5e76\u4e14\u901a\u8fc71<\/sup>H NMR\u68c0\u6d4b\u53d1\u73b0\u81ea\u7531\u57fa\u4e2d\u95f4\u4f539<\/strong>\u7684\u5b58\u5728\uff08Scheme 3a\uff09\uff0c\u4ece\u800c\u8bc1\u660e\u4e86\u81ea\u7531\u57fa\u673a\u7406\u3002\u540c\u65f6\uff0c\u4f7f\u7528\u7898\u4ee3\u70f710<\/strong>\u8fdb\u884c\u81ea\u7531\u57fa\u53cd\u5e94\uff0c\u83b7\u5f9786\uff05\u6536\u7387\u7684\u73af\u5316\u4ea7\u726911<\/strong>\uff08Scheme 3b\uff09\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u76f8\u5173\u5b9e\u9a8c\u5236\u5907\u4e86\u7532\u7845\u70f7\u57fa\u94dc\u7269\u79cdIPrCu-SiMe2<\/sub>Ph\u4e2d\u95f4\u4f5313<\/strong>\uff0c\u5e76\u5728CO\u4e0e\u4f2f\u70f7\u57fa\u7898\uff081a<\/strong>\uff09\u548c\u53d4\u70f7\u57fa\u7898\uff081u<\/strong>\uff09\u8fdb\u884c\u76f8\u5173\u53cd\u5e94\uff0c\u5206\u522b\u83b7\u5f9754\uff05\u548c99\uff05\u6536\u7387\u7684\u9170\u57fa\u7845\u70f7\uff08Scheme 3c\uff09\uff0c\u8868\u660e\u7532\u7845\u70f7\u57fa\u94dc\u4e2d\u95f4\u4f53\u53ef\u4fc3\u8fdb\u4f2f\u548c\u53d4\u70f7\u57fa\u7898\u7684\u5355\u7535\u5b50\u8f6c\u79fb\u8fc7\u7a0b\uff0c\u8fdb\u800c\u8fdb\u884c\u81ea\u7531\u57fa\u7fb0\u57fa\u5316\u53cd\u5e94\u3002\u6b64\u5916\uff0c\u7531\u4e8e\u4f2f\uff0c\u4ef2\u548c\u53d4\u70f7\u57fa\u7898\u4e4b\u95f4\u5b58\u5728\u7684\u7ade\u4e89\u5173\u7cfb\uff0c\u56e0\u6b64\u4f5c\u8005\u5bf9\u53cd\u5e94\u7684\u76f8\u5bf9\u901f\u7387\u4e5f\u8fdb\u884c\u4e86\u7814\u7a76\uff0c\u4f46\u53cd\u5e94\u7ed3\u679c\u83b7\u5f97\u76f8\u4f3c\u7684\u6536\u7387\u4ea7\u7269\uff08Scheme 3d\uff09\u3002<\/p>\n \u6839\u636e\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u548c\u76f8\u5173\u6587\u732e\u7684\u67e5\u9605\uff0c\u4f5c\u8005\u63d0\u51fa\u4e86\u4e00\u79cd\u53ef\u80fd\u7684\u53cd\u5e94\u673a\u7406\uff08Scheme 4\uff09\u3002\u9996\u5148\uff0c\u901a\u8fc7PhMe2<\/sub>Si-Bpin\u4e0eIPrCuOPh\uff08\u7531IPrCuCl\u548cNaOPh\u5f62\u6210\uff09\u53cd\u5e94\u751f\u6210\u7532\u7845\u70f7\u57fa\u94dc(I)\u914d\u5408\u7269A<\/strong>\u3002\u968f\u540e\uff0c\u914d\u5408\u7269A<\/strong>\u548c\u70f7\u57fa\u5364\u5316\u7269\u4e4b\u95f4\u7684\u8fdb\u884c\u5355\u7535\u5b50\u8f6c\u79fb\uff08SET\uff09\uff0c\u5f62\u6210\u7532\u7845\u70f7\u57fa\u94dc(II)\u914d\u5408\u7269B<\/strong>\u548c\u4e00\u4e2a\u70f7\u57fa\u81ea\u7531\u57faR\u00b7<\/strong>\u3002\u7d27\u63a5\u7740\uff0c\u81ea\u7531\u57faR\u00b7<\/strong>\u8fdb\u884c\u7fb0\u57fa\u5316\u53cd\u5e94\uff0c\u5f97\u5230\u9170\u57fa\u81ea\u7531\u57faC<\/strong>\uff0c\u518d\u4e0e\u94dc(II)\u914d\u5408\u7269B<\/strong>\u914d\u4f4d\uff0c\u5f62\u6210\u94dc(III)\u4e2d\u95f4\u4f53D<\/strong>\u3002\u6700\u540e\uff0c\u7ecf\u8fd8\u539f\u6d88\u9664\u5f97\u5230\u9170\u57fa\u7845\u70f7\uff0c\u540c\u65f6\u518d\u751f\u94dc(I)\u50ac\u5316\u5242\uff0c\u4ece\u800c\u5b9e\u73b0\u50ac\u5316\u5faa\u73af\u3002<\/p>\n<\/a><\/p>\n
\u6b63\u6587<\/h4>\n
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