{"id":51941,"date":"2024-12-31T08:00:35","date_gmt":"2024-12-31T00:00:35","guid":{"rendered":"\/\/www.gsbet888.com\/?p=51941"},"modified":"2024-12-31T09:05:51","modified_gmt":"2024-12-31T01:05:51","slug":"jacs%ef%bc%9a%e9%80%89%e6%8b%a9%e6%80%a7nii-niiii%e5%b7%a5%e8%89%ba%e7%94%a8%e4%ba%8e%e8%bf%9e%e7%bb%ad%e5%81%95csp3%e2%88%92csp2%e9%94%ae%e7%9a%84%e6%9e%84%e5%bb%ba","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2024\/12\/jacs%ef%bc%9a%e9%80%89%e6%8b%a9%e6%80%a7nii-niiii%e5%b7%a5%e8%89%ba%e7%94%a8%e4%ba%8e%e8%bf%9e%e7%bb%ad%e5%81%95csp3%e2%88%92csp2%e9%94%ae%e7%9a%84%e6%9e%84%e5%bb%ba.html","title":{"rendered":"JACS\uff1a\u9009\u62e9\u6027Ni(I)\/Ni(III)\u5de5\u827a\u7528\u4e8e\u8fde\u7eed\u5055C(sp3)\u2212C(sp2)\u952e\u7684\u6784\u5efa"},"content":{"rendered":"

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

\u5bfc\u8bfb\uff1a<\/h4>\n

\u8fd1\u65e5\uff0c\u4e0a\u6d77\u79d1\u6280\u5927\u5b66\u7684\u53f6\u67cf\u534e\u8bfe\u9898\u7ec4\u5728J. Am. Chem. Soc.<\/em>\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u5f00\u53d1\u4e00\u79cd\u5168\u65b0\u7684\u8fde\u7eed\u5f00\u58f3\u8fd8\u539f\u954d\u50ac\u5316\u4f53\u7cfb\uff0c\u4fc3\u8fdb\u4e86\u4e24\u79cd\u7acb\u4f53\u7535\u6027(stereoelectronically)\u76f8\u4f3cC(sp2<\/sup>)-I\u53cd\u5e94\u7269\u4e0e\u4e9a\u7532\u57fa\u4eb2\u7535\u8bd5\u5242\u7684\u53cd\u5e94\uff0c\u5b9e\u73b0\u4e86\u5055C(sp3<\/sup>)\u2212C(sp2<\/sup>)\u952e\u7684\u6784\u5efa\u3002\u5176\u4e2d\uff0c\u8be5\u7b56\u7565\u4ee5zirconaaziridine\u4e0e\u5143\u7d20Mg0<\/sup>\u4f5c\u4e3a\u8fd8\u539f\u5242\uff0c\u5177\u6709\u5e7f\u6cdb\u7684\u5e95\u7269\u8303\u56f4\u4ee5\u53ca\u9002\u7528\u6027\u3002\u52a8\u529b\u5b66\u7814\u7a76\u8868\u660e\uff0c\u5728\u954d\u50ac\u5316\u4e2d\uff0czirconaaziridine-\u4ecb\u5bfc\u7684\u6c27\u5316\u8fd8\u539f-\u8f6c\u91d1\u5c5e\u5316\u8fc7\u7a0b\u4fc3\u8fdb\u4e86\u53cc\u91cd\u201c\u4e32\u8054\u8fd8\u539f\u201d\u50ac\u5316\u8fc7\u7a0b\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0cNi(I)-I\u5728C(sp2<\/sup>)-I\u952e\u4e0a\u7684\u534f\u540c\u6c27\u5316\u52a0\u6210\uff0c\u4ee5\u53ca\u901a\u8fc7\u5f00\u58f3C(sp2<\/sup>)-Ni(I)\u914d\u5408\u7269\u5728\u5404\u79cdC(sp3<\/sup>)\u4eb2\u7535\u8bd5\u5242\u8fdb\u884c\u5364\u7d20\u539f\u5b50\u652b\u53d6\uff0c\u5747\u5177\u6709\u9ad8\u5ea6\u7684\u9009\u62e9\u9009\u62e9\u6027\u3002<\/p>\n

Selective Ni(I)\/Ni(III) Process for Consecutive Geminal C(sp3<\/sup>)\u2212C(sp2<\/sup>) Bond Formation<\/p>\n

X. Li, Y. Gan, Y. Wang, B. Ye, J. Am. Chem. Soc.<\/em> 2024<\/strong>, ASAP. doi: 10.1021\/jacs.4c12581<\/a>.<\/u><\/p><\/blockquote>\n

\u00a0\"\"<\/p>\n

\u6b63\u6587\uff1a<\/h4>\n

\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u7684\u591a\u7ec4\u5206\u53cd\u5e94\u5728\u539f\u5b50\u4e0e\u6b65\u9aa4\u7ecf\u6d4e\u65b9\u9762\u5177\u6709\u663e\u8457\u4f18\u52bf\uff0c\u80fd\u591f\u5728\u5355\u53cd\u5e94\u64cd\u4f5c\u4e2d\u4ece\u591a\u79cd\u8d77\u59cb\u5e95\u7269\u9ad8\u6548\u6784\u5efa\u590d\u6742\u7684\u5206\u5b50\u9aa8\u67b6\u3002\u7136\u800c\uff0c\u7531\u4e8e\u8fd9\u4e9b\u50ac\u5316\u4f53\u7cfb\u56fa\u6709\u7684\u590d\u6742\u6027\uff0c\u901a\u5e38\u6d89\u53ca\u4e24\u4e2a\u6216\u591a\u4e2a\u50ac\u5316\u5faa\u73af\u7684\u8fc7\u7a0b\uff0c\u53ef\u80fd\u4f1a\u5bfc\u81f4\u4e25\u91cd\u7684\u526f\u53cd\u5e94\uff0c\u4ece\u800c\u9650\u5236\u4e86\u53cd\u5e94\u7684\u5e94\u7528\u3002\u76ee\u524d\uff0c\u5316\u5b66\u5bb6\u4eec\u5df2\u7ecf\u6210\u529f\u5efa\u7acb\u4e86\u591a\u79cd\u8fc7\u6e21\u91d1\u5c5e\u3001\u7535\u5316\u5b66\u6216\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u5242\u4fc3\u8fdb\u70ef\u70c3\u7684\u53cc\u5b98\u80fd\u5316\u53cd\u5e94[1]<\/sup>(Scheme 1A)\u3002\u540c\u65f6\uff0c\u73b0\u6709\u7684\u65b9\u6cd5\u901a\u5e38\u4f9d\u8d56\u4e8e\u91d1\u5c5e\u5361\u5bbe\u5316\u5b66\uff0c\u5229\u7528\u91cd\u6c2e\u916f\u4f5c\u4e3a\u6709\u6548\u7684\u5355\u78b3\u66ff\u4ee3\u54c1\u3002<\/p>\n

\u954d\u50ac\u5316\u7684\u8fd8\u539f\u6027\u4ea4\u53c9\u4eb2\u7535\u5076\u8054(XEC)\u53cd\u5e94\u5df2\u6210\u4e3a\u4e00\u79cd\u4ece\u6709\u673a\u4eb2\u7535\u8bd5\u5242\u4e2d\u6784\u5efa\u78b3-\u78b3\u952e\u7684\u5f3a\u5927\u5408\u6210\u65b9\u6cd5\u30022014\u5e74\uff0cWeix\u8bfe\u9898\u7ec4\u5f00\u53d1\u4e86\u4e00\u79cd\u954d\u50ac\u5316\u82b3\u57fa\/\u70f7\u57fa\u6eb4\u7684XEC\uff0c\u5728Fe(CO)5<\/sub>\u4f5c\u4e3a\u7fb0\u57fa\u66ff\u4ee3\u7269\u7684\u5b58\u5728\u4e0b\uff0c\u4ee5\u4ea4\u53c9\u9009\u62e9\u6027\u7684\u65b9\u5f0f\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u975e\u5bf9\u79f0\u916e[2]<\/sup>\u3002\u540c\u65f6\uff0c\u4f7f\u7528\u6c2f\u7532\u9178\u916f\u4f5c\u4e3aCO\u524d\u4f53\u4e5f\u662f\u6709\u6548\u7684[3]<\/sup>\uff0c\u901a\u8fc7\u5355\u4e00\u64cd\u4f5c\u6210\u529f\u5408\u6210\u4e86\u76f8\u5e94\u7684\u70f7\u57fa-\u70f7\u57fa\u3001\u82b3\u57fa-\u70f7\u57fa\u916e\u4e0eC<\/em>-\u9170\u57fa\u7cd6\u82f7(Scheme 1B)\u3002\u7136\u800c\uff0c\u5728\u4e9a\u7532\u57faCH2<\/sub>\u5355\u5143\u4e0a\u8fde\u7eed\u5f15\u5165\u4e24\u4e2a\u6709\u673a\u5355\u5143\u7684\u53cc\u91cdXEC\u5de5\u827a\uff0c\u5374\u8f83\u5c11\u6709\u76f8\u5173\u7684\u7814\u7a76\u62a5\u9053\u3002\u4f20\u7edf\u4e0a\uff0c\u6784\u5efa\u6b64\u7c7b\u9aa8\u67b6\u5e38\u4f9d\u8d56\u4e8eSuzuki-Miyaura\u53cd\u5e94\uff0c\u8981\u6c42\u5728\u50ac\u5316\u4e4b\u524d\u9010\u6b65\u5236\u5907\u76f8\u5e94\u7684\u6709\u673a\u5364\u5316\u7269\u4e0e\u787c\u9178\u916f[4]<\/sup>(Scheme 1C)\u3002\u4f5c\u4e3a\u5bf9\u5176\u4ed6\u7ecf\u5178\u4ea4\u53c9\u5076\u8054\u65b9\u6cd5\u7684\u8865\u5145\uff0c\u8fd8\u5efa\u7acb\u4e86\u954d\u50ac\u5316\u82ef\u7532\u919a\u4e0e\u82c4\u57fa\u9541\u8bd5\u5242\u7684Kumada\u53cd\u5e94[5]<\/sup>\u3002\u53e6\u4e00\u65b9\u9762\uff0c\u4f7f\u7528\u82c4\u57fa\u4e0e\u82b3\u9999\u65cf\u4eb2\u7535\u8bd5\u5242\u8fdb\u884c\u7684\u8fd8\u539f\u6027\u954d\u50ac\u5316\u63d0\u4f9b\u4e86\u4e00\u79cd\u4f18\u8d8a\u7684\u89e3\u51b3\u65b9\u6848\uff0c\u907f\u514d\u4e86\u8f6c\u91d1\u5c5e\u5316\u5076\u8054\u8bd5\u5242\u7684\u5236\u5907[6]<\/sup>\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8fd8\u539f\u5242\u7684\u9009\u62e9\u5c06\u663e\u8457\u5f71\u54cd\u50ac\u5316\u9014\u5f84\u3002\u9664\u4e86\u8fd9\u4e9b\u7b56\u7565\u5916\uff0c\u8fd8\u63a2\u7d22\u4e86\u57fa\u4e8e\u78b3-\u6c22\u6216\u78b3-\u6742\u539f\u5b50\u952e\u7684\u76f4\u63a5\u5b98\u80fd\u5316\u7684\u65b9\u6cd5[7]<\/sup>\uff0c\u5c3d\u7ba1\u4f4d\u70b9\u9009\u62e9\u6027\u4ecd\u7136\u5b58\u5728\u6311\u6218\u3002\u524d\u671f\uff0cZirconaziridine\u4f5c\u4e3a\u4e00\u79cd\u6709\u6548\u7684\u6c27\u5316\u8fd8\u539f\u8f6c\u91d1\u5c5e\u5316\u6709\u673a\u91d1\u5c5e\u8bd5\u5242\uff0c\u80fd\u591f\u5b9e\u73b0\u94af\u50ac\u5316\u7684(\u6742)\u82b3\u9999\u5364\u7684\u4ea4\u53c9\u4eb2\u7535\u5076\u8054\u53cd\u5e94[8]<\/sup>\u4ee5\u53ca\u954d\u50ac\u5316\u975e\u5bf9\u6620\u9009\u62e9\u6027C(sp2<\/sup>)\u7cd6\u57fa\u5316\u53cd\u5e94[51]<\/sup>\u3002\u53d7\u6b64\u542f\u53d1\uff0c\u8fd9\u91cc\uff0c\u4e0a\u6d77\u79d1\u6280\u5927\u5b66\u7684\u53f6\u67cf\u534e\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u8fde\u7eed\u5f00\u58f3\u8fd8\u539f\u954d\u50ac\u5316\u4f53\u7cfb\uff0c\u4fc3\u8fdb\u4e86\u4e24\u79cd\u7acb\u4f53\u7535\u6027\u76f8\u4f3c\u7684C(sp2<\/sup>)-I\u53cd\u5e94\u7269\u4e0e\u4e9a\u7532\u57fa\u4eb2\u7535\u8bd5\u5242\u7684\u53cd\u5e94\uff0c\u5b9e\u73b0\u4e86\u5055C(sp3<\/sup>)\u2212C(sp2<\/sup>)\u952e\u7684\u6784\u5efa(Scheme 1D)\u3002\"\"<\/p>\n

\u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u8461\u8404\u7cd6\u7898\u5316\u7269(1a<\/strong>)\u4e0e\u5bf9\u7898\u5f02\u4e19\u919a(3a<\/strong>)\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Scheme 2)\u3002\u8fdb\u800c\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u75282b<\/strong>\u4f5c\u4e3a\u4e9a\u7532\u57fa\u4eb2\u7535\u8bd5\u5242\uff0cL2<\/strong>-NiBr2<\/sub>\u4f5c\u4e3a\u50ac\u5316\u5242\uff0c[Zr]\u4e0eMg0<\/sup>\u4f5c\u4e3a\u8fd8\u539f\u5242\uff0c\u5728THF\u53cd\u5e94\u6eb6\u5242\u4e2d\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a25 o<\/sup>C\uff0c\u6700\u7ec8\u83b7\u5f9777%\u6536\u7387\u7684\u4ea7\u72694<\/strong>\uff0c\u4ea4\u53c9\u9009\u62e9\u6027\u4e3a95%\u3002\u5176\u4e2d\uff0cMg0<\/sup>\u7684\u5f15\u5165\u5bfc\u81f4\u8054\u82b3\u57fahomo-3a<\/strong>\u7684\u589e\u52a0\u4ee5\u53ca\u75d5\u91cf\u7684homo-INT-1a<\/strong>\u3002\"\"<\/p>\n

\u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u5bf9\u4e00\u7cfb\u5217\u4eb2\u7535\u8bd5\u5242\u7684\u5e95\u7269\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76(Scheme 3)\u3002\u9996\u5148\uff0c\u4e00\u7cfb\u5217\u4e0d\u540c\u7535\u6027\u53d6\u4ee3\u7684\u82b3\u57fa\u4e0e\u6742\u82b3\u57fa\u7898\uff0c\u5747\u53ef\u4e0e1a<\/strong>\u4e0e2b<\/strong>\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72694<\/strong>–26<\/strong>\uff0c\u6536\u7387\u4e3a38-77%\uff0c\u4ea4\u53c9\u9009\u62e9\u6027\u4e3a82-100% (Scheme 3A)\u3002\u5176\u6b21\uff0c\u5404\u79cd\u70ef\u57fa\u6eb4\u4eb2\u7535\u8bd5\u5242\uff0c\u4e5f\u80fd\u591f\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u726927<\/strong>–34<\/strong>\uff0c\u6536\u7387\u4e3a45-76%\uff0c\u4ea4\u53c9\u9009\u62e9\u6027\u4e3a89-100% (Scheme 3B)\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u70ef\u4e19\u919a(31<\/strong>–32<\/strong>)\u4e0e\u80fa(33<\/strong>)\u9aa8\u67b6\u5728\u8be5\u6761\u4ef6\u4e0b\u53ef\u4fdd\u6301\u5b8c\u6574\u3002\u6b64\u5916\uff0c\u8be5\u7b56\u7565\u8fd8\u53ef\u7528\u4e8e\u4e00\u4e9b\u6e90\u81ea\u6c28\u57fa\u9178\u3001\u6838\u82f7\u4e0e\u5929\u7136\u4ea7\u7269\u7684\u533b\u5b66\u76f8\u5173\u4eb2\u7535\u8bd5\u5242\u7684\u540e\u671f\u884d\u751f\u5316\u5b9e\u9a8c\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u726934<\/strong>–43<\/strong>\uff0c\u6536\u7387\u4e3a39-75%\uff0c\u4ea4\u53c9\u9009\u62e9\u6027\u4e3a82-100% (Scheme 3C)\u3002\"\"<\/p>\n

\u4e4b\u540e\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5229\u7528\u8be5\u7b56\u7565\uff0c\u8fd8\u53ef\u5b9e\u73b0\u4e86\u975e\u5bf9\u79f0\u8054\u82b3\u57fa\u7532\u70f7\u7684\u5408\u6210\uff0c\u598244-55<\/strong>\uff0c\u6536\u7387\u4e3a41-86%\uff0c\u4ea4\u53c9\u9009\u62e9\u6027\u4e3a84-96%(Scheme 4A)\u3002\u7136\u800c\uff0c\u5728\u5f00\u53d1\u7684\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u75281,1-\u4e8c\u6eb4\u620a\u70f7\u4ee3\u66ff\u6807\u51c6\u7684\u4e9a\u7532\u57fa\u4eb2\u7535\u8bd5\u52422c<\/strong>\u4ecd\u7136\u5177\u6709\u6311\u6218\u6027\uff0c\u53ea\u5f97\u5230\u75d5\u91cf\u7684\u5076\u8054\u4ea7\u7269\u3002\u5176\u6b21\uff0c\u8be5\u4e09\u7ec4\u5206XEC\u4e3a\u7ecf\u5178\u70ef\u4e19\u57fa\u5316\u63d0\u4f9b\u4e86\u4e00\u79cd\u6709\u4ef7\u503c\u7684\u66ff\u4ee3\u65b9\u6848\uff0c\u53ef\u4ee5\u5408\u6210\u5404\u79cd\u70ef\u4e19\u57fa\u82ef(56<\/strong>)\u4e0e1-\u70ef\u4e19\u57fa\u70ef\u7cd6(57<\/strong>–61<\/strong>)\u884d\u751f\u7269\uff0c\u6536\u7387\u4e3a32-67%\uff0c\u4ea4\u53c9\u9009\u62e9\u6027\u4e3a81-100%(Scheme 4B)\u3002\u6b64\u5916\uff0c\u8be5\u7b56\u7565\u8fd8\u53ef\u5728\u751f\u7269\u6d3b\u6027\u5206\u5b50\u4e0a\u5b9e\u73b0\u4e86\u82c4\u57fa\u5355\u5143\u7684\u540e\u671f\u5f15\u5165(62<\/strong>–65<\/strong>)\u3002\u5728\u5bf9C<\/em>-\u7cd6\u57fa\u5316\u5316\u5408\u726966<\/strong>\u8fdb\u884c\u540e\u4fee\u9970\u540e\uff0c\u53ef\u4ee5\u5f88\u5bb9\u6613\u5730\u83b7\u5f97\u6f5c\u5728\u7684SGLT2\u6291\u5236\u5242C<\/em>-\u8461\u8404\u7cd6\u82f769<\/strong>\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u4f7f\u7528\u4e24\u79cd\u4e0d\u540c\u7684\u7cd6\u57fa\u5316\u7898\u5316\u7269(67<\/strong>)\u8fdb\u884c\u53cd\u5e94\u65f6\uff0c\u5728\u787c\u6c22\u5316\u6c27\u5316\u8fc7\u7a0b\u540e\uff0c\u53ef\u4ee597%\u7684\u9009\u62e9\u6027\u5f62\u6210C<\/em>-\u4e8c\u7cd670<\/strong>\u3002\u540c\u65f6\uff0c\u901a\u8fc7\u5bf9\u6742\u73af\u5316\u5408\u726971<\/strong>(\u5176\u662f\u5408\u6210\u4e19\u70ef\u7684\u6f5c\u5728\u4e2d\u95f4\u4f53)\u7684\u9010\u6b65\u5408\u6210\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002\"\"<\/p>\n

\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u5bf9\u4e09\u7ec4\u5206\u954d\u50ac\u5316\u4e2d\u4ea4\u53c9\u9009\u62e9\u6027\u7684\u8d77\u6e90\u8fdb\u884c\u4e86\u7814\u7a76 (Scheme 5)\u3002\u9996\u5148\uff0c\u52a8\u529b\u5b66\u7814\u7a76\u53d1\u73b0\uff0c\u954d\u50ac\u5316\u5242\u4e0eC(sp3<\/sup>)\u4eb2\u7535\u8bd5\u5242\u5448\u6b63\u4e00\u7ea7\u4f9d\u8d56\u6027\uff0c\u8868\u660e\u5b83\u4eec\u5728\u901f\u7387\u51b3\u5b9a\u6b65\u9aa4\u4e2d\u7684\u5173\u952e\u4f5c\u7528\uff0c\u53ef\u80fd\u6d89\u53ca\u7528C(sp3<\/sup>)\u7898\u5316\u7269\u4e0e\u4f4e\u4ef7Ni(I)\u914d\u5408\u7269\u4e4b\u95f4\u7684\u5364\u539f\u5b50\u652b\u53d6\u3002\u540c\u65f6\uff0c\u50ac\u5316\u901f\u7387\u53ef\u80fd\u4f1a\u53d7\u5230C(sp2<\/sup>)\u4eb2\u7535\u8bd5\u5242\u9009\u62e9\u7684\u5f71\u54cd\uff0c\u5373\u4f7f\u5b83\u4eec\u4e0d\u53c2\u4e0e\u901f\u7387\u51b3\u5b9a\u6b65\u9aa4(Scheme 5A)\u3002\u5176\u6b21\uff0c\u901a\u8fc7\u4e00\u7cfb\u5217\u7ade\u4e89\u6027\u5b9e\u9a8c\u8fdb\u884cHammett plot\u7814\u7a76\u8868\u660e\uff0cNi(I)\u5728C(sp2<\/sup>)-I\u952e\u4e0a\u8fdb\u884c\u534f\u540c\u6c27\u5316\u52a0\u6210\u3002\u66f4\u91cd\u8981\u7684\u662f\uff0czirconaaziridine\u5728\u5f00\u58f3\u954d\u50ac\u5316\u4e2d\u8d77\u7740\u5173\u952e\u4f5c\u7528\uff0c\u80fd\u591f\u9009\u62e9\u6027\u533a\u5206\u4e24\u79cd\u4e0d\u540c\u7684C(sp2<\/sup>)-I\u4eb2\u7535\u8bd5\u5242(Scheme 5B)\u3002\u53cd\u5e94\u901f\u7387\u53d6\u51b3\u4e8e\u82b3\u57fa\u7898\u4eb2\u7535\u8bd5\u5242\u7684\u7535\u5b50\u6027\u8d28\u3002\u4e00\u822c\u6765\u8bf4\uff0c\u5728\u82b3\u70c3\u4e0a\u66f4\u5927\u7684\u7535\u6027\u5dee\u5f02\u5bfc\u81f4\u4e24\u4e2a\u82b3\u57faC(sp2<\/sup>)-I\u952e\u4e4b\u95f4\u7684\u952e\u79bb\u89e3\u80fd\u5dee\u5f02\u66f4\u5927\uff0c\u4ece\u800c\u5bfc\u81f4\u66f4\u9ad8\u7684\u4ea4\u53c9\u9009\u62e9\u6027(Scheme 5C)\u3002\u7898\u5316\u805a\u7cd61b<\/strong>\u7684\u7ade\u4e89\u6027\u5b9e\u9a8c\uff0c\u5f62\u6210\u7684C(sp3<\/sup>)\u4eb2\u7535\u4e2d\u95f4\u4f53\u7684\u53cd\u5e94\u6027\u5728\u968f\u540e\u7684XEC\u5faa\u73af\u4e2d\u8d77\u7740\u5173\u952e\u7684\u4f5c\u7528\uff0c\u8fd9\u4e5f\u53ef\u80fd\u5f71\u54cd\u53cd\u5e94\u7ed3\u679c(Scheme 5D)\u3002\"\"<\/p>\n

\u57fa\u4e8e\u5bf9\u4e0a\u8ff0C(sp2<\/sup>)\u7898\u5316\u7269\u53cd\u5e94\u6027\u7684\u673a\u7406\u89c1\u89e3\uff0c\u968f\u540e\u4f5c\u8005\u5bf9\u6d89\u53ca\u5404\u79cdC(sp3<\/sup>)\u4eb2\u7535\u8bd5\u5242\u8fdb\u884c\u4e86\u4e00\u7cfb\u5217\u7ade\u4e89\u6027\u5b9e\u9a8c\u7814\u7a76(Scheme 6A)\u3002\u5b9e\u9a8c\u7ed3\u679c\u8868\u660e\uff0czirconaaziridine-\u4ecb\u5bfc\u7684XEC\u80fd\u591f\u533a\u5206\u5404\u79cdC(sp3<\/sup>)\u4eb2\u7535\u8bd5\u5242\u3002\u5176\u6b21\uff0c\u954d\u50ac\u5316PhI\u4e0e2a<\/strong>\u4ea4\u53c9\u5076\u8054\u7684\u521d\u59cb\u53cd\u5e94\u901f\u7387\u6bd4nhex-I\u5feb46\u500d(Scheme 6B)\u3002\u53cd\u5e94\u6027\u7684\u663e\u8457\u5dee\u5f02\u53ef\u80fd\u5f52\u56e0\u4e8e2a<\/strong>\u7684C(sp3<\/sup>)-I\u952e\u8f83\u5f31\uff0c\u8fd9\u5728\u70ed\u529b\u5b66\u4e0a\u6709\u5229\u4e8e\u901a\u8fc7\u4f4e\u4ef7Ni(I)\u914d\u5408\u7269\u5bf9\u7898\u5316\u7269\u8fdb\u884c\u652b\u53d6\u5f62\u6210\u66f4\u7a33\u5b9a\u7684C(sp3<\/sup>)\u81ea\u7531\u57fa\u3002\u56e0\u6b64\uff0c2a<\/strong>\u7684\u5feb\u901f\u521d\u59cbXEC\u50ac\u5316\u6709\u6548\u5730\u6291\u5236\u4e86\u4e0d\u671f\u671b\u7684\u81ea\u5076\u8054\u3002\u9664\u4e86\u4e0a\u8ff0\u7814\u7a76\u5916\uff0c\u4f5c\u8005\u8fd8\u8fdb\u884c\u4e86\u4e00\u7cfb\u5217\u5bf9\u7167\u5b9e\u9a8c\u6765\u9610\u660eMg0<\/sup>\u7684\u4f5c\u7528\u3002Mg0<\/sup>\u53ef\u80fd\u4fc3\u8fdb\u4e86\u70ef\u4e19\u57fa\u6216\u82c4\u57fa\u7898\u4e2d\u95f4\u4f53\u7684\u5355\u7535\u5b50\u8fd8\u539f\uff0c\u751f\u6210\u76f8\u5e94\u7684C(sp3<\/sup>)\u81ea\u7531\u57fa\u4e2d\u95f4\u4f53\uff0c\u5728\u7b2c\u4e8c\u4e2aXEC\u50ac\u5316\u5faa\u73af\u4e2d\u91cd\u7ec4\u4e3aC(sp2<\/sup>)-Ni(II)\u4e2d\u95f4\u4f53(Scheme 6C)\u3002\u540c\u65f6\uff0c\u5364\u76d0\u53ef\u80fd\u4f5c\u4e3a\u6dfb\u52a0\u5242\uff0c\u53ef\u4ee5\u52a0\u901fNi(II)\u7684\u8fd8\u539f\u8fc7\u7a0b\u3002<\/p>\n

\u57fa\u4e8e\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u7814\u7a76\uff0c\u4f5c\u8005\u63d0\u51fa\u5982\u4e0b\u5408\u7406\u7684\u53cd\u5e94\u673a\u7406 (Scheme 6D)\u3002\u5728\u7b2c\u4e00\u4e2a\u50ac\u5316\u5faa\u73af\u4e2d\uff0cNi(I)-I\u914d\u5408\u7269A<\/strong>\u6c27\u5316\u52a0\u6210\u5230\u4e24\u79cdC(sp2<\/sup>)\u7898\u5316\u7269\u4e2d\u7684\u4e00\u79cd\uff0c\u5176\u4e2d\u89c2\u5bdf\u5230\u7684\u9009\u62e9\u6027\u53ef\u5f52\u56e0\u4e8eC(sp2<\/sup>)-\u7898\u5316\u7269\u4e4b\u95f4\u7684\u952e\u5f3a\u5ea6\u5dee\u5f02\u53ca\u5176\u521d\u59cb\u6d53\u5ea6\u7684\u5dee\u5f02\u3002\u63a5\u4e0b\u6765\uff0c\u7528Cp2<\/sub>Zr(III)\u8fd8\u539f\u6240\u5f97\u7684C(sp2<\/sup>)-Ni(III)\u914d\u5408\u7269B<\/strong>\u5c06\u751f\u6210C(sp2<\/sup>)-Ni(II)\u4e2d\u95f4\u4f53C<\/strong>\u3002\u968f\u540e\uff0c\u4e2d\u95f4\u4f53C\u901a\u8fc7\u6c27\u5316\u8fd8\u539f\u8f6c\u91d1\u5c5e\u5316\u8fc7\u7a0b\uff0c\u53ef\u5c06\u5176\u5316\u4e3a\u4f4e\u4ef7\u53cc\u91d1\u5c5eNi-Zr\u914d\u5408\u7269D<\/strong>\u3002\u7136\u540e\uff0c\u8fd9\u79cd\u5173\u952e\u7684\u5f00\u58f3Ni(I)\u914d\u5408\u7269\u53ef\u80fd\u4f1a\u901a\u8fc7\u8bbe\u60f3\u7684\u5364\u539f\u5b50\u652b\u53d6\u4e0e\u4e9a\u7532\u57fa\u4eb2\u7535\u8bd5\u52422<\/strong>\u53cd\u5e94\uff0c\u751f\u6210\u81ea\u7531\u57fa\u7ed3\u5408\u7684Ni(II)\u4e2d\u95f4\u4f53E<\/strong>\u3002\u6700\u540e\uff0c\u5728\u81ea\u7531\u57fa\u91cd\u7ec4\u540e\uff0c\u5f62\u6210\u7684C(sp2<\/sup>)-Ni(III)-C(sp3<\/sup>)\u914d\u5408\u7269F<\/strong>\u3002\u914d\u5408\u7269F<\/strong>\u7ecf\u8fd8\u539f\u6d88\u9664\uff0c\u751f\u6210C(sp2<\/sup>)-CH2<\/sub>-OTs\u4e2d\u95f4\u4f53\u3002\u5728\u4e32\u8054\u7684XEC\u5faa\u73af\u4e2d\uff0cMg0<\/sup>\u53ef\u80fd\u4f5c\u4e3a\u5f3a\u6548\u5355\u7535\u5b50\u8fd8\u539f\u5242\u3002\u5728\u78b3\u81ea\u7531\u57fa\u91cd\u7ec4\u4e3aC(sp2<\/sup>)-Ni(II)\u914d\u5408\u7269H<\/strong>\u540e\uff0c\u968f\u540e\u8fd8\u539f\u6d88\u9664Ni(III)\u914d\u5408\u7269J<\/strong>\u4ece\u800c\u83b7\u5f97\u6240\u9700\u7684\u4ea4\u53c9\u5076\u8054\u4ea7\u7269\uff0c\u540c\u65f6\u518d\u751f\u4e86Ni(I)-I\u914d\u5408\u7269A<\/strong>\u3002\"\"<\/p>\n

\u603b\u7ed3\uff1a<\/h4>\n

\u4e0a\u6d77\u79d1\u6280\u5927\u5b66\u7684\u53f6\u67cf\u534e\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u7531\u9009\u62e9\u6027\u5f00\u58f3\u954d\u50ac\u5316\u4f53\u7cfb\u4fc3\u8fdb\u7684\u4e09\u7ec4\u5206XEC\u53cd\u5e94\u3002\u5728\u8fd9\u79cd\u65b9\u6cd5\u4e2d\uff0czirconaaziridine\u5145\u5f53\u4e00\u79cd\u5f3a\u5927\u7684\u6c27\u5316\u8fd8\u539f\u8f6c\u91d1\u5c5e\u5316\u8bd5\u5242\uff0c\u4ea7\u751f\u4f4e\u4ef7C(sp2<\/sup>)-Ni(I)\u914d\u5408\u7269\uff0c\u4fc3\u8fdb\u5728\u901f\u7387\u51b3\u5b9a\u6b65\u9aa4\u4e2d\u9009\u62e9\u6027\u533a\u5206\u5404\u79cdC(sp3<\/sup>)\u4eb2\u7535\u8bd5\u5242\u3002\u6b64\u5916\uff0c\u5728Ni(I)-I\u534f\u540c\u6c27\u5316\u52a0\u6210\u8fc7\u7a0b\u4e2d\u533a\u5206\u4e24\u79cd\u4e0d\u540c\u7684C(sp2<\/sup>)-\u7898\u5316\u7269\u7684\u80fd\u529b\u5bf9\u4e8e\u5b9e\u73b0\u9ad8\u4ea4\u53c9\u9009\u62e9\u6027\u81f3\u5173\u91cd\u8981\u3002\u00a0<\/strong><\/p>\n

\u53c2\u8003\u6587\u732e\uff1a<\/strong><\/h4>\n

[1] J. Z. Wang, W. L. Lyon, D. W. C. MacMillan, Nature <\/em>2024<\/strong>, 628<\/em>, 104. doi:<\/p>\n

10.1038\/s41586-024-07165-x<\/a>.<\/p>\n

[2] A. C. Wotal, R. D. Ribson, D. J. Weix, Organometallics <\/em>2014<\/strong>, 33<\/em>, 5874. doi:<\/p>\n

10.1021\/om5004682<\/a>.<\/p>\n

[3] R. Shi, X. Hu, Angew. Chem., Int. Ed. <\/em>2019<\/strong>, 58<\/em>, 7454. doi:10.1002\/anie.201903330<\/a>.<\/p>\n

[4] M. Nambo, E. C. Keske, J. P. G. Rygus, J. C. H. Yim, C. M. Crudden, ACS Catal. <\/em>2017<\/strong>, 7<\/em>, 1108. doi:10.1021\/acscatal.6b03434<\/a>.<\/p>\n

[5] M. Tobisu, T. Takahira, N. Chatani, Org. Lett. <\/em>2015<\/strong>, 17<\/em>, 4352. doi:10.1021\/acs.orglett.5b02200<\/a>.<\/p>\n

[6] J. Zhang, G. Lu, J. Xu, H. Sun, Q. Shen, Org. Lett. <\/em>2016<\/strong>, 18<\/em>, 2860. doi:10.1021\/acs.orglett.6b01134<\/a>.<\/p>\n

[7] P. R. Ledwith, M. L. Cooney, K. A. Bahou, J. Garcia-Carceles, J. Thomson, J. Bower, Angew. Chem., Int. Ed. <\/em>2024<\/strong>, 63<\/em>, No. e202411555. doi:10.1002\/anie.202411555<\/a>.<\/p>\n

[8] T. Wu, Y. Zhang, Y. Fu, F. Liu, J. Tang, P. Liu, F. D. Toste, B. Ye, Chem <\/em>2021<\/strong>, 7<\/em>, 1963. doi:10.1016\/j.chempr.2021.06.007<\/a>.<\/p>\n

[9] Y. Gan, J. Zhou, X. Li, J. Liu, F. Liu, X. Hong, B. Ye, J. Am. Chem. Soc. <\/em>2024<\/strong>, 146<\/em>, 16753. doi:10.1021\/jacs.4c04587<\/a>.<\/p>\n

\u672c\u6587\u7248\u6743\u5c5e\u4e8e\u00a0Chem-Station\u5316\u5b66\u7a7a\u95f4\uff0c \u6b22\u8fce\u70b9\u51fb\u6309\u94ae\u5206\u4eab\uff0c\u672a\u7ecf\u8bb8\u53ef\uff0c\u8c22\u7edd\u8f6c\u8f7d.<\/p>\n

\u5173\u6ce8Chem-Station\u6296\u97f3\u53f7\uff1a79473891841<\/p>\n

\u8bf7\u767b\u9646TCI\u8bd5\u5242\u5b98\u7f51\u67e5\u770b\u66f4\u591a\u5185\u5bb9<\/h5>\n
https:\/\/www.tcichemicals.com\/CN\/zh\/<\/h5>\n

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Li, Y. Gan, Y. Wang, B. Ye, J. Am. Chem. Soc. 2024, ASAP. doi: 10.1021\/jacs.4c12581. \u00a0 \u6b63\u6587\uff1a 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1B)\u3002\u7136\u800c\uff0c\u5728\u4e9a\u7532\u57faCH2\u5355\u5143\u4e0a\u8fde\u7eed\u5f15\u5165\u4e24\u4e2a\u6709\u673a\u5355\u5143\u7684\u53cc\u91cdXEC\u5de5\u827a\uff0c\u5374\u8f83\u5c11\u6709\u76f8\u5173\u7684\u7814\u7a76\u62a5\u9053\u3002\u4f20\u7edf\u4e0a\uff0c\u6784\u5efa\u6b64\u7c7b\u9aa8\u67b6\u5e38\u4f9d\u8d56\u4e8eSuzuki-Miyaura\u53cd\u5e94\uff0c\u8981\u6c42\u5728\u50ac\u5316\u4e4b\u524d\u9010\u6b65\u5236\u5907\u76f8\u5e94\u7684\u6709\u673a\u5364\u5316\u7269\u4e0e\u787c\u9178\u916f[4](Scheme 1C)\u3002\u4f5c\u4e3a\u5bf9\u5176\u4ed6\u7ecf\u5178\u4ea4\u53c9\u5076\u8054\u65b9\u6cd5\u7684\u8865\u5145\uff0c\u8fd8\u5efa\u7acb\u4e86\u954d\u50ac\u5316\u82ef\u7532\u919a\u4e0e\u82c4\u57fa\u9541\u8bd5\u5242\u7684Kumada\u53cd\u5e94[5]\u3002\u53e6\u4e00\u65b9\u9762\uff0c\u4f7f\u7528\u82c4\u57fa\u4e0e\u82b3\u9999\u65cf\u4eb2\u7535\u8bd5\u5242\u8fdb\u884c\u7684\u8fd8\u539f\u6027\u954d\u50ac\u5316\u63d0\u4f9b\u4e86\u4e00\u79cd\u4f18\u8d8a\u7684\u89e3\u51b3\u65b9\u6848\uff0c\u907f\u514d\u4e86\u8f6c\u91d1\u5c5e\u5316\u5076\u8054\u8bd5\u5242\u7684\u5236\u5907[6]\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8fd8\u539f\u5242\u7684\u9009\u62e9\u5c06\u663e\u8457\u5f71\u54cd\u50ac\u5316\u9014\u5f84\u3002\u9664\u4e86\u8fd9\u4e9b\u7b56\u7565\u5916\uff0c\u8fd8\u63a2\u7d22\u4e86\u57fa\u4e8e\u78b3-\u6c22\u6216\u78b3-\u6742\u539f\u5b50\u952e\u7684\u76f4\u63a5\u5b98\u80fd\u5316\u7684\u65b9\u6cd5[7]\uff0c\u5c3d\u7ba1\u4f4d\u70b9\u9009\u62e9\u6027\u4ecd\u7136\u5b58\u5728\u6311\u6218\u3002\u524d\u671f\uff0cZirconaziridine\u4f5c\u4e3a\u4e00\u79cd\u6709\u6548\u7684\u6c27\u5316\u8fd8\u539f\u8f6c\u91d1\u5c5e\u5316\u6709\u673a\u91d1\u5c5e\u8bd5\u5242\uff0c\u80fd\u591f\u5b9e\u73b0\u94af\u50ac\u5316\u7684(\u6742)\u82b3\u9999\u5364\u7684\u4ea4\u53c9\u4eb2\u7535\u5076\u8054\u53cd\u5e94[8]\u4ee5\u53ca\u954d\u50ac\u5316\u975e\u5bf9\u6620\u9009\u62e9\u6027C(sp2)\u7cd6\u57fa\u5316\u53cd\u5e94[51]\u3002\u53d7\u6b64\u542f\u53d1\uff0c\u8fd9\u91cc\uff0c\u4e0a\u6d77\u79d1\u6280\u5927\u5b66\u7684\u53f6\u67cf\u534e\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u8fde\u7eed\u5f00\u58f3\u8fd8\u539f\u954d\u50ac\u5316\u4f53\u7cfb\uff0c\u4fc3\u8fdb\u4e86\u4e24\u79cd\u7acb\u4f53\u7535\u6027\u76f8\u4f3c\u7684C(sp2)-I\u53cd\u5e94\u7269\u4e0e\u4e9a\u7532\u57fa\u4eb2\u7535\u8bd5\u5242\u7684\u53cd\u5e94\uff0c\u5b9e\u73b0\u4e86\u5055C(sp3)\u2212C(sp2)\u952e\u7684\u6784\u5efa(Scheme 1D)\u3002 \u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u8461\u8404\u7cd6\u7898\u5316\u7269(1a)\u4e0e\u5bf9\u7898\u5f02\u4e19\u919a(3a)\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Scheme 2)\u3002\u8fdb\u800c\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u75282b\u4f5c\u4e3a\u4e9a\u7532\u57fa\u4eb2\u7535\u8bd5\u5242\uff0cL2-NiBr2\u4f5c\u4e3a\u50ac\u5316\u5242\uff0c[Zr]\u4e0eMg0\u4f5c\u4e3a\u8fd8\u539f\u5242\uff0c\u5728THF\u53cd\u5e94\u6eb6\u5242\u4e2d\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a25 oC\uff0c\u6700\u7ec8\u83b7\u5f9777%\u6536\u7387\u7684\u4ea7\u72694\uff0c\u4ea4\u53c9\u9009\u62e9\u6027\u4e3a95%\u3002\u5176\u4e2d\uff0cMg0\u7684\u5f15\u5165\u5bfc\u81f4\u8054\u82b3\u57fahomo-3a\u7684\u589e\u52a0\u4ee5\u53ca\u75d5\u91cf\u7684homo-INT-1a\u3002 \u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u5bf9\u4e00\u7cfb\u5217\u4eb2\u7535\u8bd5\u5242\u7684\u5e95\u7269\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76(Scheme 3)\u3002\u9996\u5148\uff0c\u4e00\u7cfb\u5217\u4e0d\u540c\u7535\u6027\u53d6\u4ee3\u7684\u82b3\u57fa\u4e0e\u6742\u82b3\u57fa\u7898\uff0c\u5747\u53ef\u4e0e1a\u4e0e2b\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72694–26\uff0c\u6536\u7387\u4e3a38-77%\uff0c\u4ea4\u53c9\u9009\u62e9\u6027\u4e3a82-100% (Scheme 3A)\u3002\u5176\u6b21\uff0c\u5404\u79cd\u70ef\u57fa\u6eb4\u4eb2\u7535\u8bd5\u5242\uff0c\u4e5f\u80fd\u591f\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u726927–34\uff0c\u6536\u7387\u4e3a45-76%\uff0c\u4ea4\u53c9\u9009\u62e9\u6027\u4e3a89-100% (Scheme 3B)\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u70ef\u4e19\u919a(31–32)\u4e0e\u80fa(33)\u9aa8\u67b6\u5728\u8be5\u6761\u4ef6\u4e0b\u53ef\u4fdd\u6301\u5b8c\u6574\u3002\u6b64\u5916\uff0c\u8be5\u7b56\u7565\u8fd8\u53ef\u7528\u4e8e\u4e00\u4e9b\u6e90\u81ea\u6c28\u57fa\u9178\u3001\u6838\u82f7\u4e0e\u5929\u7136\u4ea7\u7269\u7684\u533b\u5b66\u76f8\u5173\u4eb2\u7535\u8bd5\u5242\u7684\u540e\u671f\u884d\u751f\u5316\u5b9e\u9a8c\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u726934–43\uff0c\u6536\u7387\u4e3a39-75%\uff0c\u4ea4\u53c9\u9009\u62e9\u6027\u4e3a82-100% (Scheme 3C)\u3002 \u4e4b\u540e\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5229\u7528\u8be5\u7b56\u7565\uff0c\u8fd8\u53ef\u5b9e\u73b0\u4e86\u975e\u5bf9\u79f0\u8054\u82b3\u57fa\u7532\u70f7\u7684\u5408\u6210\uff0c\u598244-55\uff0c\u6536\u7387\u4e3a41-86%\uff0c\u4ea4\u53c9\u9009\u62e9\u6027\u4e3a84-96%(Scheme 4A)\u3002\u7136\u800c\uff0c\u5728\u5f00\u53d1\u7684\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u75281,1-\u4e8c\u6eb4\u620a\u70f7\u4ee3\u66ff\u6807\u51c6\u7684\u4e9a\u7532\u57fa\u4eb2\u7535\u8bd5\u52422c\u4ecd\u7136\u5177\u6709\u6311\u6218\u6027\uff0c\u53ea\u5f97\u5230\u75d5\u91cf\u7684\u5076\u8054\u4ea7\u7269\u3002\u5176\u6b21\uff0c\u8be5\u4e09\u7ec4\u5206XEC\u4e3a\u7ecf\u5178\u70ef\u4e19\u57fa\u5316\u63d0\u4f9b\u4e86\u4e00\u79cd\u6709\u4ef7\u503c\u7684\u66ff\u4ee3\u65b9\u6848\uff0c\u53ef\u4ee5\u5408\u6210\u5404\u79cd\u70ef\u4e19\u57fa\u82ef(56)\u4e0e1-\u70ef\u4e19\u57fa\u70ef\u7cd6(57–61)\u884d\u751f\u7269\uff0c\u6536\u7387\u4e3a32-67%\uff0c\u4ea4\u53c9\u9009\u62e9\u6027\u4e3a81-100%(Scheme 4B)\u3002\u6b64\u5916\uff0c\u8be5\u7b56\u7565\u8fd8\u53ef\u5728\u751f\u7269\u6d3b\u6027\u5206\u5b50\u4e0a\u5b9e\u73b0\u4e86\u82c4\u57fa\u5355\u5143\u7684\u540e\u671f\u5f15\u5165(62–65)\u3002\u5728\u5bf9C-\u7cd6\u57fa\u5316\u5316\u5408\u726966\u8fdb\u884c\u540e\u4fee\u9970\u540e\uff0c\u53ef\u4ee5\u5f88\u5bb9\u6613\u5730\u83b7\u5f97\u6f5c\u5728\u7684SGLT2\u6291\u5236\u5242C-\u8461\u8404\u7cd6\u82f769\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u4f7f\u7528\u4e24\u79cd\u4e0d\u540c\u7684\u7cd6\u57fa\u5316\u7898\u5316\u7269(67)\u8fdb\u884c\u53cd\u5e94\u65f6\uff0c\u5728\u787c\u6c22\u5316\u6c27\u5316\u8fc7\u7a0b\u540e\uff0c\u53ef\u4ee597%\u7684\u9009\u62e9\u6027\u5f62\u6210C-\u4e8c\u7cd670\u3002\u540c\u65f6\uff0c\u901a\u8fc7\u5bf9\u6742\u73af\u5316\u5408\u726971(\u5176\u662f\u5408\u6210\u4e19\u70ef\u7684\u6f5c\u5728\u4e2d\u95f4\u4f53)\u7684\u9010\u6b65\u5408\u6210\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002 \u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u5bf9\u4e09\u7ec4\u5206\u954d\u50ac\u5316\u4e2d\u4ea4\u53c9\u9009\u62e9\u6027\u7684\u8d77\u6e90\u8fdb\u884c\u4e86\u7814\u7a76 (Scheme 5)\u3002\u9996\u5148\uff0c\u52a8\u529b\u5b66\u7814\u7a76\u53d1\u73b0\uff0c\u954d\u50ac\u5316\u5242\u4e0eC(sp3)\u4eb2\u7535\u8bd5\u5242\u5448\u6b63\u4e00\u7ea7\u4f9d\u8d56\u6027\uff0c\u8868\u660e\u5b83\u4eec\u5728\u901f\u7387\u51b3\u5b9a\u6b65\u9aa4\u4e2d\u7684\u5173\u952e\u4f5c\u7528\uff0c\u53ef\u80fd\u6d89\u53ca\u7528C(sp3)\u7898\u5316\u7269\u4e0e\u4f4e\u4ef7Ni(I)\u914d\u5408\u7269\u4e4b\u95f4\u7684\u5364\u539f\u5b50\u652b\u53d6\u3002\u540c\u65f6\uff0c\u50ac\u5316\u901f\u7387\u53ef\u80fd\u4f1a\u53d7\u5230C(sp2)\u4eb2\u7535\u8bd5\u5242\u9009\u62e9\u7684\u5f71\u54cd\uff0c\u5373\u4f7f\u5b83\u4eec\u4e0d\u53c2\u4e0e\u901f\u7387\u51b3\u5b9a\u6b65\u9aa4(Scheme 5A)\u3002\u5176\u6b21\uff0c\u901a\u8fc7\u4e00\u7cfb\u5217\u7ade\u4e89\u6027\u5b9e\u9a8c\u8fdb\u884cHammett plot\u7814\u7a76\u8868\u660e\uff0cNi(I)\u5728C(sp2)-I\u952e\u4e0a\u8fdb\u884c\u534f\u540c\u6c27\u5316\u52a0\u6210\u3002\u66f4\u91cd\u8981\u7684\u662f\uff0czirconaaziridine\u5728\u5f00\u58f3\u954d\u50ac\u5316\u4e2d\u8d77\u7740\u5173\u952e\u4f5c\u7528\uff0c\u80fd\u591f\u9009\u62e9\u6027\u533a\u5206\u4e24\u79cd\u4e0d\u540c\u7684C(sp2)-I\u4eb2\u7535\u8bd5\u5242(Scheme 5B)\u3002\u53cd\u5e94\u901f\u7387\u53d6\u51b3\u4e8e\u82b3\u57fa\u7898\u4eb2\u7535\u8bd5\u5242\u7684\u7535\u5b50\u6027\u8d28\u3002\u4e00\u822c\u6765\u8bf4\uff0c\u5728\u82b3\u70c3\u4e0a\u66f4\u5927\u7684\u7535\u6027\u5dee\u5f02\u5bfc\u81f4\u4e24\u4e2a\u82b3\u57faC(sp2)-I\u952e\u4e4b\u95f4\u7684\u952e\u79bb\u89e3\u80fd\u5dee\u5f02\u66f4\u5927\uff0c\u4ece\u800c\u5bfc\u81f4\u66f4\u9ad8\u7684\u4ea4\u53c9\u9009\u62e9\u6027(Scheme 5C)\u3002\u7898\u5316\u805a\u7cd61b\u7684\u7ade\u4e89\u6027\u5b9e\u9a8c\uff0c\u5f62\u6210\u7684C(sp3)\u4eb2\u7535\u4e2d\u95f4\u4f53\u7684\u53cd\u5e94\u6027\u5728\u968f\u540e\u7684XEC\u5faa\u73af\u4e2d\u8d77\u7740\u5173\u952e\u7684\u4f5c\u7528\uff0c\u8fd9\u4e5f\u53ef\u80fd\u5f71\u54cd\u53cd\u5e94\u7ed3\u679c(Scheme 5D)\u3002 \u57fa\u4e8e\u5bf9\u4e0a\u8ff0C(sp2)\u7898\u5316\u7269\u53cd\u5e94\u6027\u7684\u673a\u7406\u89c1\u89e3\uff0c\u968f\u540e\u4f5c\u8005\u5bf9\u6d89\u53ca\u5404\u79cdC(sp3)\u4eb2\u7535\u8bd5\u5242\u8fdb\u884c\u4e86\u4e00\u7cfb\u5217\u7ade\u4e89\u6027\u5b9e\u9a8c\u7814\u7a76(Scheme 6A)\u3002\u5b9e\u9a8c\u7ed3\u679c\u8868\u660e\uff0czirconaaziridine-\u4ecb\u5bfc\u7684XEC\u80fd\u591f\u533a\u5206\u5404\u79cdC(sp3)\u4eb2\u7535\u8bd5\u5242\u3002\u5176\u6b21\uff0c\u954d\u50ac\u5316PhI\u4e0e2a\u4ea4\u53c9\u5076\u8054\u7684\u521d\u59cb\u53cd\u5e94\u901f\u7387\u6bd4nhex-I\u5feb46\u500d(Scheme 6B)\u3002\u53cd\u5e94\u6027\u7684\u663e\u8457\u5dee\u5f02\u53ef\u80fd\u5f52\u56e0\u4e8e2a\u7684C(sp3)-I\u952e\u8f83\u5f31\uff0c\u8fd9\u5728\u70ed\u529b\u5b66\u4e0a\u6709\u5229\u4e8e\u901a\u8fc7\u4f4e\u4ef7Ni(I)\u914d\u5408\u7269\u5bf9\u7898\u5316\u7269\u8fdb\u884c\u652b\u53d6\u5f62\u6210\u66f4\u7a33\u5b9a\u7684C(sp3)\u81ea\u7531\u57fa\u3002\u56e0\u6b64\uff0c2a\u7684\u5feb\u901f\u521d\u59cbXEC\u50ac\u5316\u6709\u6548\u5730\u6291\u5236\u4e86\u4e0d\u671f\u671b\u7684\u81ea\u5076\u8054\u3002\u9664\u4e86\u4e0a\u8ff0\u7814\u7a76\u5916\uff0c\u4f5c\u8005\u8fd8\u8fdb\u884c\u4e86\u4e00\u7cfb\u5217\u5bf9\u7167\u5b9e\u9a8c\u6765\u9610\u660eMg0\u7684\u4f5c\u7528\u3002Mg0\u53ef\u80fd\u4fc3\u8fdb\u4e86\u70ef\u4e19\u57fa\u6216\u82c4\u57fa\u7898\u4e2d\u95f4\u4f53\u7684\u5355\u7535\u5b50\u8fd8\u539f\uff0c\u751f\u6210\u76f8\u5e94\u7684C(sp3)\u81ea\u7531\u57fa\u4e2d\u95f4\u4f53\uff0c\u5728\u7b2c\u4e8c\u4e2aXEC\u50ac\u5316\u5faa\u73af\u4e2d\u91cd\u7ec4\u4e3aC(sp2)-Ni(II)\u4e2d\u95f4\u4f53(Scheme 6C)\u3002\u540c\u65f6\uff0c\u5364\u76d0\u53ef\u80fd\u4f5c\u4e3a\u6dfb\u52a0\u5242\uff0c\u53ef\u4ee5\u52a0\u901fNi(II)\u7684\u8fd8\u539f\u8fc7\u7a0b\u3002 \u57fa\u4e8e\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u7814\u7a76\uff0c\u4f5c\u8005\u63d0\u51fa\u5982\u4e0b\u5408\u7406\u7684\u53cd\u5e94\u673a\u7406 (Scheme 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Z. Wang, W. L. Lyon, D. W. C. MacMillan, Nature 2024, 628, 104. doi: 10.1038\/s41586-024-07165-x. [2] A. C. Wotal, R. D. Ribson, D. J. Weix, Organometallics 2014, 33, 5874. doi: 10.1021\/om5004682. [3] R. Shi, X. 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