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\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749<\/p>\n
\u5e95\u7269\u5bfc\u5411\u7684\u4e0d\u5bf9\u79f0\u53cd\u5e94\uff0c\u56e0\u80fd\u591f\u4ece\u5ec9\u4ef7\u6613\u5f97\u7684\u8d77\u59cb\u539f\u6599\u4e2d\u7cbe\u786e\u6784\u7b51\u7acb\u4f53\u4e2d\u5fc3\u800c\u500d\u53d7\u8d5e\u8a89\uff0c\u5176\u88ab\u5e7f\u6cdb\u7528\u4e8e\u73b0\u4ee3\u6709\u673a\u5408\u6210\u4e2d\u3002\u8fc7\u53bb\u5341\u5e74\u91cc\uff0c\u5316\u5b66\u5bb6\u5f00\u521b\u4e86\u5bfc\u5411\u57fa\u56e2\u5b9e\u73b0\u60f0\u6027\u70c3\u7684\u5bf9\u6620\u9009\u62e9\u6027C(sp3<\/sup>)-H\u5b98\u80fd\u5316\u53cd\u5e94\u7684\u65b0\u9014\u5f84\uff0c\u4f7f\u5f97\u7b80\u5355\u7684\u5316\u5b66\u5206\u5b50\u53d8\u5f97\u590d\u6742\u3002\u8fc4\u4eca\u4e3a\u6b62\uff0c\u7531\u4e8e\u5316\u5b66\u5206\u5b50\u7684\u590d\u6742\u6027\uff0c\u4f7f\u5f97\u8fd9\u79cd\u65b9\u6cd5\u5e76\u672a\u6210\u529f\u3002\u5c3d\u7ba1\u6e38\u79bb\u7684\u8102\u80aa\u65cf\u4f2f\u80fa\u662f\u6709\u673a\u5408\u6210\u4e2d\u901a\u7528\u7684\u4e2d\u95f4\u4f53\uff0c\u4f46\u5728\u4f20\u7edf\u7684C(sp3<\/sup>)-H\u6d3b\u5316\u53cd\u5e94\u4e2d\u5747\u4e0d\u53cd\u5e94\uff0c\u800c\u4e14\u5728\u94af\u50ac\u5316\u7684\u78b3\u6c22\u6d3b\u5316\u53cd\u5e94\u4e2d\u4f2f\u80fa\u5f80\u5f80\u4f1a\u5bfc\u81f4\u50ac\u5316\u5242\u5931\u6d3b\u3002\u56e0\u6b64\uff0c\u5982\u4f55\u5728\u4e0d\u9002\u7528\u4fdd\u62a4\u57fa\u56e2\u7684\u524d\u63d0\u4e0b\uff0c\u5b9e\u73b0\u8fd9\u7c7b\u5e95\u7269\u7684\u4e0d\u5bf9\u79f0\u78b3\u6c22\u952e\u6d3b\u5316\u4ecd\u662f\u6446\u5728\u79d1\u5b66\u5bb6\u9762\u524d\u7684\u96be\u9898\u3002\u8fd1\u65e5\uff0c\u7f8e\u56fdScripps\u7814\u7a76\u6240\u4f59\u91d1\u6743\u6559\u6388\u8bfe\u9898\u7ec4\u5728\u7f8e\u56fd\u5316\u5b66\u5b66\u4f1a\u6742\u5fd7\u4e0a\uff08Journal of the American Chemical Society\uff09\u53d1\u8868\u8bba\u6587\uff0c\u901a\u8fc7\u4f7f\u7528\u624b\u6027\u53cc\u9f7f\u4e8c\u786b\u4ee3\u919a\u914d\u4f53\uff0c\u5b9e\u73b0\u4e86Pd\u50ac\u5316\u6e38\u79bb\u8102\u80aa\u65cf\u4f2f\u80fa\uff08\u73af\u4e19\u57fa\u7532\u57fa\u80fa\uff09\u7684\u5bf9\u6620\u9009\u62e9\u6027C(sp3<\/sup>)-H\u5b98\u80fd\u5316\u3002\u8be5\u914d\u4f53\u7279\u6709\u7684\u53cc\u9f7f\u914d\u4f4d\u6a21\u5f0f\u548c\u786b\u919a\u57fa\u56e2\uff0c\u6709\u52a9\u4e8e\u751f\u6210\u5173\u952e\u7684\u5355(\u80fa)-Pd(II)\u4e2d\u95f4\u4f53\uff0c\u4ece\u800c\u5b9e\u73b0\u4e86\u5bf9\u6e38\u79bb\u80fa\u7684\u5bf9\u6620\u9009\u62e9\u6027C-H\u952e\u6d3b\u5316\u3002\u6b64\u5916\uff0c\u751f\u6210\u7684C-Pd(II)\u914d\u5408\u7269\u53ef\u53c2\u4e0ePd(II)\/Pd(IV)\u6216Pd(II)\/Pd(0)\u50ac\u5316\u5faa\u73af\uff0c\u5e76\u901a\u8fc7\uff08\u6742\uff09\u82b3\u57fa\u5316\u3001\u7fb0\u57fa\u5316\u548c\u70ef\u5316\u53cd\u5e94\uff0c\u4ece\u800c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u7269\u3002\u8be5\u6cd5\u591a\u6837\u7684\u53cd\u5e94\u6027\u4e3a\u836f\u7269\u5316\u5b66\u5bb6\u63d0\u4f9b\u4e86\u4e00\u79cd\u5feb\u901f\u5236\u5907\u529f\u80fd\u5316\u751f\u7269\u76f8\u5173\u80fa\u7684\u901a\u7528\u7b56\u7565\u3002<\/p>\n Pd(II)-Catalyzed Enantioselective \u03b3<\/em>-C(sp3<\/sup>)\u2212H Functionalizations of Free Cyclopropylmethylamines<\/p>\n Zhe Zhuang, and Jin-Quan Yu*<\/p>\n J. Am. Chem. Soc.<\/em> ASAP DOI:10.1021\/jacs.0c04801<\/a><\/p><\/blockquote>\n 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1A\uff09\u3002\u5c3d\u7ba1DG\u6216TDG\u7b56\u7565\u90fd\u5f88\u7cbe\u81f4\uff0c\u4f46\u7531\u4e8e\u53cc\u9f7f\u5bfc\u5411\u57fa\u56e2\u6781\u5f3a\u7684\u914d\u4f4d\u80fd\u529b\u5bfc\u81f4\u624b\u6027\u914d\u4f53\u65e0\u53ef\u7528\u7684\u914d\u4f4d\u70b9\uff0c\u5f88\u96be\u5b9e\u73b0\u5bf9\u6620\u9009\u62e9\u6027\u3002\u540c\u65f6\uff0c\u7531\u4e8e\u7f3a\u4e4f\u7a7a\u7684\u914d\u4f4d\u70b9\uff0c\u5bfc\u81f4\u8be5\u53cd\u5e94\u4e3b\u8981\u96c6\u4e2d\u4e8ePd(II)\/Pd(IV)\u50ac\u5316\u5faa\u73af\u4e2d\uff0c\u5bf9\u4e8ePd(II)\/Pd(0)\u7684\u5faa\u73af\u5374\u5f88\u5c11\u88ab\u62a5\u9053\u3002\u5bf9\u5e95\u7269DG\u7684\u8981\u6c42\u6392\u9664\u4e86\u4f7f\u7528\u5929\u7136\u6c28\u57fa\u6765\u6307\u5bfcC-H\u6d3b\u5316\u7684\u53ef\u80fd\u6027\uff0c\u8fd9\u5728\u65e0\u4fdd\u62a4\u57fa\u5408\u6210\u7684\u60c5\u51b5\u4e0b\u63d0\u4f9b\u4e86\u4f18\u5f02\u7684\u539f\u5b50\u548c\u6b65\u957f\u7ecf\u6d4e\u6027\u3002\u636e\u62a5\u9053\uff0c\u6e38\u79bb\u7684\u8102\u80aa\u80fa\u76f4\u63a5\u8fdb\u884cC-H\u5b98\u80fd\u5316\u53cd\u5e94\u4e3b\u8981\u9650\u4e8e\u4f53\u79ef\u8f83\u5927\u7684\u80fa\uff0c\u9700\u8981\u5728\u6e38\u79bb\u80fa\u7684\u03b1<\/em>\u4f4d\u7f6e\u5f62\u6210\u4e00\u4e2a\u5e9e\u5927\u7684\u57fa\u56e2\uff0c\u4ee5\u4fc3\u8fdb\u53cc(\u80fa)-Pd(II)\u914d\u5408\u7269\u901a\u8fc7\u7a7a\u95f4\u6392\u65a5\u800c\u89e3\u79bb\uff0c\u4ece\u800c\u963b\u6b62\u6c27\u5316\u964d\u89e3\u4ee5\u53ca\u524a\u5f31\u6c28\u57fa\u7684\u4eb2\u6838\u6027\uff08Scheme 1A\uff09\u3002<\/p>\n \u57fa\u4e8e\u5bf9\u5355\u9f7fDGs\u548c\u53cc\u9f7f\u914d\u4f53\u7684\u7ed3\u5408\u6765\u5b9e\u73b0\u5bf9\u6620\u9009\u62e9\u6027C-H\u6d3b\u5316\u53cd\u5e94\u7684\u6301\u7eed\u7814\u7a76\uff0c\u4f5c\u8005\u8bd5\u56fe\u5c06\u66f4\u5177\u6709\u6311\u6218\u6027\u7684\u5316\u5b66\u539f\u6599\uff08\u5982\u8102\u80aa\u65cf\u4f2f\u80fa\uff09\u5e94\u7528\u5230\u6b64\u4f53\u7cfb\u4e2d\uff08Scheme 1B\uff09\u3002\u4e3a\u4e86\u89e3\u79bb\u7a33\u5b9a\u7684\u53cc(\u80fa)-Pd(II)\u914d\u5408\u7269\uff0c\u9700\u52a0\u5165\u989d\u5916\u7684\u914d\u4f53\u4ee5\u4fc3\u8fdb\u751f\u6210\u5177\u6709\u53cd\u5e94\u6027\u7684\u5355(\u80fa)-Pd(II)\u4e2d\u95f4\u4f53\u3002\u56e0\u6b64\uff0c\u8be5\u914d\u4f53\u7684\u8bbe\u8ba1\u5bf9\u4e8e\u53cd\u5e94\u81f3\u5173\u91cd\u8981\u3002\u6b64\u5916\uff0c\u914d\u4f53\u4e0a\u7684\u9170\u80fa\u57fa\u56e2\uff08N<\/em>-\u9170\u57fa\uff09\u4e0d\u4ec5\u4f5c\u4e3a\u5185\u90e8\u78b1\uff08\u901a\u8fc7\u6d88\u9664\u03b2<\/em>-\u6c22\u5316\u7269\u6765\u4fc3\u8fdbC(sp3<\/sup>)-H\u6d3b\u5316\uff09\uff0c\u540c\u65f6\u5b83\u4e5f\u8db3\u591f\u4e0d\u7a33\u5b9a\uff08\u53ef\u4e3aPd(II)\/Pd(0)\u50ac\u5316\u5faa\u73af\u4e2d\u751f\u6210\u4e00\u4e2a\u7a7a\u4f4d\u7684\u914d\u4f4d\u70b9\uff09\u3002\u5728\u672c\u6587\u4e2d\uff0c\u4f5c\u8005\u62a5\u9053\u4e86\u57fa\u4e8e\u786b\u919a\u7684\u624b\u6027\u53cc\u9f7f\u914d\u4f53\u7684\u8bbe\u8ba1\uff0c\u8be5\u914d\u4f53\u80fd\u591f\u5b9e\u73b0Pd(II)\u50ac\u5316\u7684\u8102\u80aa\u65cf\u73af\u4e19\u57fa\u7532\u4f2f\u80fa\u7684\u5bf9\u6620\u9009\u62e9\u6027C-H\u529f\u80fd\u5316\u53cd\u5e94\uff08Scheme 1C\uff09\u3002\u901a\u8fc7Pd(II)\/Pd(IV)\u50ac\u5316\u5faa\u73af\u8fdb\u884c\u4e19\u70ef\u9178\u5316\u53cd\u5e94\uff0c\u5f97\u5230\u03b3-<\/em>\u53d6\u4ee3\u82b3\u57fa\u4ea7\u7269\uff0c\u5305\u62ec\u6c2e\u6742\u73af\u7684\u624b\u6027\u6e38\u79bb\u8102\u80aa\u80fa\u7b49\u3002\u540c\u65f6\uff0c\u8be5\u50ac\u5316\u5242\u80fd\u591f\u901a\u8fc7Pd(II)\/Pd(0)\u50ac\u5316\u5faa\u73af\u4f7f\u4f2f\uff08\u4ef2\uff09\u6e38\u79bb\u80fa\u8fdb\u884c\u70ef\u5316\u548c\u7fb0\u57fa\u5316\u53cd\u5e94\uff0c\u5206\u522b\u83b7\u5f97\u5177\u6709\u4ef7\u503c\u7684\u03b3<\/em>-\u70ef\u5316\u6e38\u79bb\u80fa\u548c\u03b3<\/em>-\u5185\u9170\u80fa\u884d\u751f\u7269\u3002<\/p>\n \u968f\u540e\uff0c\u4f5c\u8005\u4ee5\u6e38\u79bb\u7684\u73af\u4e19\u57fa\u7532\u80fa1a<\/strong>\u548c4-\u7898\u7532\u82ef2a<\/strong>\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u5bf9\u914d\u4f53\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u7b5b\u9009\uff08Table 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2\uff09\u3002\u4e3a\u4e86\u65b9\u4fbf\u7eaf\u5316\u548c\u5206\u6790\uff0c\u03b3<\/em>-\u82b3\u57fa\u5316\u4ea7\u7269\u4e2d\u7684\u6c28\u57fa\u5747\u4ee5\u53d4\u4e01\u6c27\u7fb0\u57fa\uff08Boc\uff09\u6216\u82ef\u7532\u9170\u57fa\uff08Bz\uff09\u4fdd\u62a4\u3002\u5728\u03b2<\/em>-\u4f4d\u5e26\u6709\u5404\u79cd\u94fe\u72b6\u8102\u80aa\u65cf\u70f7\u70c3\uff0c\u751a\u81f3\u73af\u4e01\u70f7\u3001<\/strong>\u73af\u620a\u70f7\u3001\u73af\u5df1\u70f7\u7b49\uff0c\u5747\u4e0e\u4f53\u7cfb\u517c\u5bb9\uff0c\u4ece\u800c\u83b7\u5f97\u76f8\u5e94\u7684\u82b3\u57fa\u5316\u4ea7\u72693b\u2019<\/sup><\/strong>–3g\u2019<\/sup><\/strong>\u3002\u540c\u65f6\uff0c\u5177\u6709\u6c1f\u3001\u4e09\u6c1f\u7532\u57fa\u3001\u56db\u6c22\u5421\u5583\u3001\u82c4\u57fa\uff08Bn\uff09\u4fdd\u62a4\u7684\u7f9f\u57fa\u3001\u7532\u6c27\u57fa\u548c\u915a\u919a\u7b49\u57fa\u56e2\uff0c\u4e5f\u53ef\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693h\u2019<\/sup><\/strong>–3m\u2019<\/sup><\/strong>\u3002\u6b64\u5916\uff0c\u542b\u6709\u5438\u7535\u5b50\u6216\u7ed9\u7535\u5b50\u57fa\u56e2\u7684\u82ef\u57fa\uff0c\u53cd\u5e94\u4e5f\u4e0d\u53d7\u5f71\u54cd\uff0c\u4ece\u800c\u83b7\u5f97\u4ea7\u72693a\u2019<\/sup><\/strong>\u548c3n\u2019<\/sup><\/strong>–3s\u2019<\/sup><\/strong>\u3002\u5bf9\u4e8e\u53cd\u5e94\u6027\u8f83\u4f4e\u7684\u672a\u53d6\u4ee3\u73af\u4e19\u57fa\u7532\u80fa\uff0c\u4e5f\u53ef\u5408\u6210\u76f8\u5e94\u7684\u4ea7\u72693t\u2019<\/sup><\/strong>\u3002\u4f46\u662f\uff0c\u5bf9\u4e8e\u73af\u4e01\u57fa\u7532\u80fa\u5e95\u7269\uff0c\u4e0d\u9002\u7528\u4e8e\u8be5\u4f53\u7cfb\u3002<\/p>\n 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3\uff09\u3002\u5e26\u6709\u7ed9\u7535\u5b50\u57fa\u56e2\u548c\u5438\u7535\u5b50\u57fa\u56e2\u7684\u7898\u4ee3\u82ef\u5e95\u7269\uff0c\u5747\u4e0e\u4f53\u7cfb\u517c\u5bb9\uff0c\u4ece\u800c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72694b\u2019<\/sup><\/strong>–4j\u2019<\/sup><\/strong>\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5177\u6709\u4e00\u4e9b\u6d3b\u6027\u7684\u57fa\u56e2\uff08\u5982\u916f\u3001\u5364\u7d20\u7b49\uff09\uff0c\u53ef\u4e3a\u540e\u671f\u4fee\u9970\u63d0\u4f9b\u591a\u79cd\u53ef\u80fd\u3002\u540c\u65f6\uff0c\u5bf9\u4e8e\u6742\u73af\u5e95\u7269\uff08\u5421\u5576\u3001\u5432\u54da\uff09\uff0c\u4e5f\u540c\u6837\u5177\u6709\u826f\u597d\u7684\u517c\u5bb9\u6027\uff0c\u4ece\u800c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72694k\u2019<\/sup>-4t\u2019<\/sup><\/strong>\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u7531\u4e8e\u786b\u914d\u4f53\u4e0e\u50ac\u5316\u5242\u7684\u5f3a\u914d\u4f4d\u6027\uff0c\u6291\u5236\u4e86\u5421\u5576\u4e0e\u94af\u7684\u914d\u4f4d\uff0c\u4ece\u800c\u4f7f\u4f4e\u6d3b\u6027\u7684\u5421\u5576\u5e95\u7269\u4e5f\u9002\u7528\u4e8e\u8be5\u4f53\u7cfb\u3002<\/p>\n 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