{"id":55370,"date":"2025-04-02T08:00:49","date_gmt":"2025-04-02T00:00:49","guid":{"rendered":"\/\/www.gsbet888.com\/?p=55370"},"modified":"2025-04-02T15:39:48","modified_gmt":"2025-04-02T07:39:48","slug":"nat-chem-%ef%bc%9a%e7%83%af%e7%83%83%e4%b8%8e%e9%a5%b1%e5%92%8c%e6%9d%82%e7%8e%af%e5%8c%96%e5%90%88%e7%89%a9%e7%9a%84%e7%9b%b4%e6%8e%a5%e7%ab%8b%e4%bd%93%e9%80%89%e6%8b%a9%e6%80%a7csp3-h","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2025\/04\/nat-chem-%ef%bc%9a%e7%83%af%e7%83%83%e4%b8%8e%e9%a5%b1%e5%92%8c%e6%9d%82%e7%8e%af%e5%8c%96%e5%90%88%e7%89%a9%e7%9a%84%e7%9b%b4%e6%8e%a5%e7%ab%8b%e4%bd%93%e9%80%89%e6%8b%a9%e6%80%a7csp3-h.html","title":{"rendered":"Nat. Chem.\uff1a\u70ef\u70c3\u4e0e\u9971\u548c\u6742\u73af\u5316\u5408\u7269\u7684\u76f4\u63a5\u7acb\u4f53\u9009\u62e9\u6027C(sp3)\u2013H\u70f7\u57fa\u5316\u53cd\u5e94"},"content":{"rendered":"

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

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

\u8fd1\u65e5\uff0c\u6b66\u6c49\u5927\u5b66\u7684\u5b54\u671b\u6e05\u8bfe\u9898\u7ec4\u5728Nat. Chem.<\/i><\/em>\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u954d\u50ac\u5316\u9971\u548c\u6742\u73af\u5316\u5408\u7269\u4e0e\u70ef\u70c3\u7684\u5bf9\u6620\u9009\u62e9\u6027C(sp<\/em>3<\/sup>)\u2013H\u70f7\u57fa\u5316\u53cd\u5e94\uff0c\u4e3aC(sp<\/em>3<\/sup>)\u2013C(sp<\/em>3<\/sup>)\u952e\u7684\u7acb\u4f53\u9009\u62e9\u6027\u6784\u5efa\u63d0\u4f9b\u4e86\u4e00\u79cd\u6709\u6548\u7684\u7b56\u7565\u3002\u5176\u4e2d\uff0c\u8be5\u7b56\u7565\u4f7f\u7528\u6613\u5f97\u4e0e\u7a33\u5b9a\u7684\u70ef\u70c3\u548c\u7b80\u5355\u7684\u9971\u548c\u6c2e\u548c\u6c27\u6742\u73af\u5316\u5408\u7269\u4f5c\u4e3a\u524d\u624b\u6027\u4eb2\u6838\u8bd5\u5242\uff0c\u5076\u8054\u53cd\u5e94\u53ef\u5728\u6e29\u548c\u7684\u6761\u4ef6\u4e0b\u8fdb\u884c\uff0c\u5e76\u8868\u73b0\u51fa\u5e7f\u6cdb\u7684\u5e95\u7269\u8303\u56f4\u4e0e\u9ad8\u5ea6\u7684\u5b98\u80fd\u56e2\u8010\u53d7\u6027\u3002\u5176\u6b21\uff0c\u4f5c\u8005\u8fd8\u5b9e\u73b0\u4e86\u9971\u548c\u70c3\u4e0e\u70ef\u57fa\u787c\u9178\u916f\u7684\u5bf9\u6620\u4e0e\u975e\u5bf9\u6620\u9009\u62e9\u6027C(sp<\/em>3<\/sup>)\u2013H\u70f7\u57fa\u5316\u53cd\u5e94\uff0c\u4ece\u800c\u5408\u6210\u4e86\u542b\u6709\u76f8\u90bb\u624b\u6027\u4e2d\u5fc3\u7684\u70f7\u57fa\u787c\u9178\u916f\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u5bf9\u5929\u7136\u4ea7\u7269\u4e0e\u836f\u7269\u5206\u5b50\u7684\u540e\u671f\u4fee\u9970\uff0c\u4ee5\u53ca\u4e00\u7cfb\u5217\u624b\u6027\u7ed3\u6784\u5355\u5143\u4e0e\u5929\u7136\u4ea7\u7269\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5408\u6210\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002<\/p>\n

\n

Direct stereoselective C(sp<\/em>3<\/sup>)\u2013H alkylation of\u00a0saturated heterocycles using olefins<\/p>\n

Z.Zhou, Y.Ke, R.\u00a0Miao, F.\u00a0Hu, X.\u00a0Wang,\u00a0Y.\u00a0Ping, S.\u00a0Xu,\u00a0W.\u00a0Kong, <\/i>Chem.<\/i><\/em>\u00a02025<\/strong>, 17<\/em>, 344. doi:\u00a010.1038\/s41557-025-01747-6<\/u>.<\/u><\/a><\/p>\n

\n<\/blockquote>\n

\"\"<\/p>\n

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

\u901a\u8fc7C(sp<\/em>3<\/sup>)\u2013H\u5b98\u80fd\u56e2\u5316\u5c06\u78b3\u6c22\u5316\u5408\u7269\u8f6c\u5316\u4e3a\u9ad8\u9644\u52a0\u503c\u7684\u624b\u6027\u5316\u5408\u7269\uff0c\u5177\u6709\u9ad8\u5ea6\u7684\u539f\u5b50\u4e0e\u6b65\u9aa4\u7ecf\u6d4e\u6027\uff0c\u4ece\u800c\u5907\u53d7\u5173\u6ce8\u3002\u7136\u800c\uff0c\u5bf9\u4e8e\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u5bf9\u6620\u9009\u62e9\u6027C(sp<\/em>3<\/sup>)\u2013H\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\uff0c\u5177\u6709\u4e00\u5b9a\u7684\u6311\u6218\u3002\u8fd1\u5e74\u6765\uff0c\u6c22\u539f\u5b50\u8f6c\u79fb(HAT, hydrogen atom\u00a0transfer)[1]<\/sup>\u4e0e\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u4ea4\u53c9\u5076\u8054[2]<\/sup>\u76f8\u7ed3\u5408\u7684\u7b56\u7565\uff0c\u5df2\u6210\u4e3a\u5b9e\u73b0C(sp<\/em>3<\/sup>)\u2013H\u952e\u8fdb\u884c\u5bf9\u6620\u9009\u62e9\u6027\u5b98\u80fd\u56e2\u5316\u7684\u6709\u529b\u5de5\u5177\u3002\u7136\u800c\uff0c\u5bf9\u4e8e\u7f3a\u4e4f\u5bfc\u5411\u57fa\u56e2\u7684\u9971\u548c\u70c3\u901a\u8fc7\u5bf9\u6620\u9009\u62e9\u6027C(sp<\/em>3<\/sup>)\u2013H\u70f7\u57fa\u5316\u53cd\u5e94\u6784\u5efaC(sp<\/em>3<\/sup>)\u2013C(sp<\/em>3<\/sup>)\u952e\u7684\u65b9\u6cd5\uff0c\u4ecd\u5177\u6709\u96be\u5ea6(Fig. 1a)\u3002\u540c\u65f6\uff0c\u624b\u6027\u9971\u548c\u6c2e\u4e0e\u6c27\u6742\u73af\u9aa8\u67b6\u5e7f\u6cdb\u5b58\u5728\u4e8e\u5404\u7c7b\u751f\u7269\u6d3b\u6027\u5206\u5b50\u4e0e\u5929\u7136\u4ea7\u7269\u7b49\u4e2d\uff0c\u82e5\u80fd\u5bf9\u5176\u8fdb\u884c\u8fdb\u4e00\u6b65\u7684\u4fee\u9970\uff0c\u5219\u66f4\u5177\u7814\u7a76\u4ef7\u503c\u3002\u76ee\u524d\uff0c\u5bf9\u4e8e\u5421\u54af\u70f7\u884d\u751f\u7269\u7684\u5bf9\u6620\u9009\u62e9\u6027C(sp<\/em>3<\/sup>)\u2013H\u70f7\u57fa\u5316\u53cd\u5e94\u4e3b\u8981\u4f9d\u8d56\u4e8eN<\/em>-(\u53d4\u4e01\u6c27\u7fb0\u57fa)\u5421\u54af\u70f7\u7684\u03b1<\/em>-\u9502\u5316\uff0c\u968f\u540e\u4e0e\u70f7\u57fa\u5364\u8fdb\u884cNegishi\u4ea4\u53c9\u5076\u8054[3]<\/sup>\uff0c\u4f46\u9700\u5728\u82db\u523b\u7684\u6761\u4ef6\u4e0b\u8fdb\u884c\u53bb\u8d28\u5b50\u5316\uff0c\u5e76\u4e14\u5bf9\u4e00\u7ea7\u70f7\u57fa\u5364\u5177\u6709\u8f83\u4f4e\u7684\u5bf9\u6620\u9009\u62e9\u6027(Fig. 1b)\u3002\u53d7\u5230\u8fd1\u5e74\u6765\u5bf9\u4e8e\u954d\u50ac\u5316\u8fc7\u6c27\u5316\u7269\u4ecb\u5bfcC(sp<\/em>3<\/sup>)\u2013H\u5b98\u80fd\u56e2\u5316[4]<\/sup>\u4e0eNiH-\u50ac\u5316\u70ef\u70c3\u52a0\u6c22\u70f7\u57fa\u5316\u53cd\u5e94[<\/sup>5<\/sup>]<\/sup>\u76f8\u5173\u7814\u7a76\u62a5\u9053\u7684\u542f\u53d1\uff0c\u8fd9\u91cc\uff0c\u6b66\u6c49\u5927\u5b66\u7684\u5b54\u671b\u6e05\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u954d\u50ac\u5316\u9971\u548c\u6742\u73af\u5316\u5408\u7269\u4e0e\u70ef\u70c3\u7684\u5bf9\u6620\u9009\u62e9\u6027C(sp<\/em>3<\/sup>)\u2013H\u70f7\u57fa\u5316\u53cd\u5e94\uff0c\u4ece\u800c\u5b9e\u73b0\u4e86C(sp<\/em>3<\/sup>)\u2013C(sp<\/em>3<\/sup>)\u952e\u7684\u7acb\u4f53\u9009\u62e9\u6027\u6784\u5efa(Fig. 1c)\u3002\u540c\u65f6\uff0c\u901a\u8fc7\u5bf9\u5929\u7136\u4ea7\u7269\u4e0e\u836f\u7269\u5206\u5b50\u7684\u540e\u671f\u4fee\u9970\uff0c\u4ee5\u53ca\u4e00\u7cfb\u5217\u624b\u6027\u7ed3\u6784\u5355\u5143\u4e0e\u5929\u7136\u4ea7\u7269\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5408\u6210\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027(Fig. 1d)\u3002<\/p>\n

\"\"<\/p>\n

\u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u5421\u54af\u70f7\u884d\u751f\u72691<\/strong>\u4e0e\u975e\u6d3b\u5316\u70ef\u70c32<\/strong>\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Table 1)\u3002\u8fdb\u800c\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u7528NiBr2<\/sub>\u00b7DME\u4f5c\u4e3a\u50ac\u5316\u5242\uff0cL8<\/strong>\u4f5c\u4e3a\u624b\u6027\u914d\u4f53\uff0c\u8fc7\u6c27\u5316\u4e8c\u5f02\u4e19\u82ef(DCP)\u4f5c\u4e3aHAT\u8bd5\u5242\u4e0e\u6c27\u5316\u5242\uff0cKHCO3<\/sub>\u4f5c\u4e3a\u78b1\uff0cZn\u7c89\u4f5c\u4e3a\u8fd8\u539f\u5242\uff0c(MeO)3<\/sub>SiH\u4f5c\u4e3a\u6c22\u6e90\uff0c\u5728EA\u53cd\u5e94\u6eb6\u5242\u4e2d\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a0 o<\/sup>C\uff0c\u6700\u7ec8\u83b7\u5f9761%\u5206\u79bb\u6536\u7387\u7684\u4ea7\u72693<\/strong>(97% ee<\/em>)\u3002\u5176\u4e2d\uff0c\u8be5\u53cd\u5e94\u6210\u529f\u7684\u5173\u952e\u662f\u627e\u5230\u4e00\u79cd\u5408\u9002\u7684HAT\u6c27\u5316\u5242\uff0c\u8be5\u6c27\u5316\u5242\u53ef\u4ee5\u4e0e\u78b3\u6c22\u5316\u5408\u7269\u5b9e\u73b0\u9ad8\u6548\u7684HAT\uff0c\u5e76\u5728\u954d\u50ac\u5316\u5faa\u73af\u4e2d\u80fd\u591f\u6c27\u5316\u954d\u3002\"\"<\/p>\n

\u00a0<\/strong>\u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u5bf9\u4e00\u7cfb\u5217\u975e\u6d3b\u5316\u70ef\u70c3\u7684\u5e95\u7269\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76(Table 2)\u3002\u9996\u5148\uff0c\u4e0a\u8ff0\u5408\u6210\u7684\u4ea7\u72693<\/strong>\u5728\u9178\u6027\u6761\u4ef6\u4e0b\uff0c\u5f88\u5bb9\u6613\u8fdb\u884c\u8131\u4fdd\u62a4\uff0c\u83b7\u5f97N-H\u5421\u54af\u70f7\u4ea7\u72695<\/strong>\u3002\u5176\u6b21\uff0c\u4e00\u7cfb\u5217\u4e0d\u540c\u53d6\u4ee3\u7684\u672b\u7aef\u70ef\u70c3\uff0c\u5747\u53ef\u4e0e\u5421\u54af\u70f7\u884d\u751f\u72691<\/strong>\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72696<\/strong>–25<\/strong>\uff0c\u6536\u7387\u4e3a39-73%\uff0cee\u4e3a89-99%\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u4e00\u7cfb\u5217\u6d3b\u6027\u7684\u57fa\u56e2\uff0c\u5982\u5364\u7d20\u3001\u7845\u57fa\u3001\u70f7\u6c27\u7fb0\u57fa\u7b49\uff0c\u5747\u4e0e\u4f53\u7cfb\u517c\u5bb9\u3002\u7136\u800c\uff0c\u542b\u6709\u6e38\u79bb\u9187\u7684\u5e95\u7269\uff0c\u672a\u80fd\u6709\u6548\u7684\u8fdb\u884c\u53cd\u5e94\u3002\u540c\u65f6\uff0c\u975e\u5bf9\u79f0\u76841,1-\u4e8c\u53d6\u4ee3\u70ef\u70c3\u8fdb\u884c\u5076\u8054\u53cd\u5e94\u65f6\uff0c\u53ef\u83b7\u5f97\u5177\u67091,3-\u975e\u76f8\u90bb\u624b\u6027\u4e2d\u5fc3\u7684\u4ea7\u7269\uff0c\u5c3d\u7ba1\u975e\u5bf9\u6620\u9009\u62e9\u6027\u8f83\u5dee\uff0c\u4f46\u4e24\u79cd\u975e\u5bf9\u6620\u5f02\u6784\u4f53\u90fd\u5177\u6709\u51fa\u8272\u7684\u5bf9\u6620\u9009\u62e9\u6027\uff0c\u598225<\/strong>\u3002\u6b64\u5916\uff0c\u73af\u70ef\u70c3\u4e5f\u662f\u5408\u9002\u7684\u5e95\u7269\uff0c\u53ef\u4ee541%\u7684\u6536\u7387\u5f97\u5230\u4ea7\u726926<\/b><\/strong>\uff0cee\u4e3a94%\u3002\u6709\u8da3\u7684\u662f\uff0c\u4f7f\u7528\u5185\u70ef\u70c3\u8fdb\u884cC(sp<\/em>3<\/sup>)\u2013C(sp<\/em>3<\/sup>)\u952e\u7684\u6784\u5efa\u65f6\uff0c\u53cd\u5e94\u53d1\u751f\u5728\u8fdc\u7aefC(sp<\/em>3<\/sup>)-H\u952e\u800c\u4e0d\u662fipso<\/em>-\u4f4d(6<\/strong>\u300127<\/strong>\u548c28<\/strong>)\uff0c\u4ece\u800c\u8868\u660e\u8be5\u53cd\u5e94\u6d89\u53ca\u954d\u6c22\u914d\u5408\u7269\u7684\u94fe\u884c\u8d70\u8fc7\u7a0b\u3002\u4f7f\u7528\u8f9b\u70ef29<\/b><\/strong>\u7684\u6df7\u5408\u7269\u8fdb\u884c\u70f7\u57fa\u5316\u53cd\u5e94\u65f6\uff0c\u53ef\u83b7\u5f97\u5355\u4e00\u7684\u533a\u57df\u5f02\u6784\u4f53\u4ea7\u72699<\/strong>\uff0cee\u4e3a97%\u3002\u7136\u800c\uff0c\u5bf9\u4e8e\u975e\u6d3b\u53161,1,2-\u4e09\u53d6\u4ee3\u6216\u56db\u53d6\u4ee3\u70ef\u70c3\uff0c\u672a\u80fd\u83b7\u5f97\u9884\u671f\u4ea7\u7269(\u598230<\/strong>)\uff0c\u53ef\u80fd\u662f\u7531\u4e8e\u7a7a\u95f4\u4f4d\u963b\u963b\u6b62\u4e86\u70ef\u70c3\u8fc1\u79fb\u63d2\u5165Ni-H\u914d\u5408\u7269\u5bfc\u81f4\u3002\"\"<\/p>\n

\u5176\u6b21\uff0c\u4f5c\u8005\u5bf9\u4e00\u7cfb\u5217C(sp<\/em>3<\/sup>)\u2013H\u7684\u5e95\u7269\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76(Table 3)\u3002\u7814\u7a76\u7ed3\u679c\u8868\u660e\uff0c\u5728\u4f18\u5316\u7684\u6761\u4ef6\u4e0b\uff0c\u5404\u79cd\u9971\u548c\u7684\u6c2e\u4e0e\u6c27\u6742\u73af\u5316\u5408\u7269\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u70f7\u57fa\u5316\u53cd\u5e94\uff0c\u5177\u6709\u826f\u597d\u7684\u6536\u7387\u4ee5\u53ca\u4f18\u5f02\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002\u5176\u4e2d\uff0c(R<\/i><\/em>)-2-\u7532\u57fa-1-\u82ef\u7532\u9170\u57fa\u5421\u54af\u70f7(33<\/b><\/strong>)\u5728\u7a7a\u95f4\u4f4d\u963b\u8f83\u5c0f\u7684C(sp<\/em>3<\/sup>)\u2013H\u952e\u4e0a\u9009\u62e9\u6027\u8fdb\u884c\u70f7\u57fa\u5316\u53cd\u5e94\uff0c\u5177\u6709\u9ad8\u5ea6\u7684\u975e\u5bf9\u6620\u9009\u62e9\u6027\u3002\u7136\u800c\uff0c\u65e0\u73afN<\/i><\/em>-\u70f7\u57fa\u82ef\u7532\u9170\u80fa\uff0c\u672a\u80fd\u83b7\u5f97\u9884\u671f\u7684\u70f7\u57fa\u5316\u4ea7\u7269\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8be5\u7b56\u7565\u8fd8\u53ef\u7528\u4e8e\u4e00\u4e9b\u5929\u7136\u4ea7\u7269\u4e0e\u836f\u7269\u5206\u5b50\u7684\u540e\u671f\u4fee\u9970\uff0c\u598247<\/b><\/strong>–55<\/b><\/strong>\u3002\"\"<\/p>\n

\u6b64\u5916\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5f53\u4ee5NiBr2<\/sub>\u00b7DME\u4f5c\u4e3a\u50ac\u5316\u5242\uff0cL2<\/strong>\u4f5c\u4e3a\u624b\u6027\u914d\u4f53\uff0c\u8fc7\u6c27\u5316\u4e8c\u53d4\u4e01\u57fa(DTBP)\u4f5c\u4e3aHAT\u8bd5\u5242\u4e0e\u6c27\u5316\u5242\uff0cCs2<\/sub>CO3<\/sub>\u4f5c\u4e3a\u78b1\uff0c\u805a\u7532\u57fa\u6c22\u7845\u6c27\u70f7(PHMS)\u4f5c\u4e3a\u6c22\u6e90\uff0c\u53ef\u4fc3\u8fdb\u70ef\u57fa\u787c\u9178\u916f\u4e0eC(sp<\/em>3<\/sup>)\u2013H\u5e95\u7269\u7684\u5bf9\u6620\u4e0e\u975e\u5bf9\u6620\u9009\u62e9\u6027\u70f7\u57fa\u5316\u53cd\u5e94(Table 4)\u3002\u8fdb\u4e00\u6b65\u7814\u7a76\u8868\u660e\uff0c\u70ef\u57fa-\u9891\u90a3\u9187\u787c\u70f7(\u70ef\u57fa-Bpin)\u5bf9\u4e8e\u8be5\u53cd\u5e94\u5177\u6709\u72ec\u7279\u4e4b\u5904\uff0c\u56e0\u4e3a\u5176\u4ed6\u6709\u673a\u787c\u8bd5\u5242\uff0c\u5982\u70ef\u57fa(1,8-\u8418\u4e8c\u6c28\u57fa)\u787c\u70f7\u548c9-\u70ef\u57fa-9-\u787c\u53cc\u73af[3.3.1]\u58ec\u70f7\uff0c\u672a\u80fd\u751f\u6210\u9884\u671f\u7684\u4ea7\u7269\u3002\u5176\u6b21\uff0c\u542b\u6709\u5404\u79cd\u5b98\u80fd\u56e2\u5316\u7684\u70ef\u70c3\uff0c\u5982\u919a\u3001TBS\u919a\u3001\u70f7\u6c27\u7fb0\u57fa\u3001\u90bb\u82ef\u4e8c\u7532\u9170\u4e9a\u80fa\u548c\u82b3\u57fa\u7b49\uff0c\u5747\u4e0e\u4f53\u7cfb\u517c\u5bb9\u3002\u6b64\u5916\uff0c\u5177\u6709\u5f3aC(sp<\/em>3<\/sup>)\u2013H\u952e\u7684\u73af\u70f7\u70c3\uff0c\u5982\u73af\u620a\u70f7(69<\/b><\/strong>)\u548c\u73af\u5df1\u70f7(70<\/b><\/strong>)\uff0c\u4e5f\u662f\u5408\u9002\u7684\u5e95\u7269\u3002\"\"<\/p>\n

\u4e4b\u540e\uff0c\u4f5c\u8005\u5bf9\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u8fdb\u884c\u4e86\u7814\u7a76 (Fig. 2)\u3002\u9996\u5148\uff0c\u4ee5\u5421\u54af\u70f7\u884d\u751f\u72691<\/b><\/strong>\u4e3a\u5e95\u7269\uff0c\u901a\u8fc7\u4e09\u6b65\u53cd\u5e94\uff0c\u53ef\u5206\u522b\u5b9e\u73b0(R<\/i><\/em>)-Bgugaine\u3001(R<\/i><\/em>)-Irnidine\u4e0e(\u2212)-Coniceine\u7684\u5168\u5408\u6210(Fig. 2a)\u3002\u5176\u6b21\uff0c\u4ee5\u4e19\u916e\u4fdd\u62a4\u76841,3-\u4e8c\u918777<\/b><\/strong>\u4e3a\u5e95\u7269\uff0c\u5229\u7528\u4e0a\u8ff0\u7684\u7b56\u7565\uff0c\u8fd8\u53ef\u5b9e\u73b0(S<\/i><\/em>)-\u786b\u8f9b\u9178\u4e0e\u00a0(\u2212)-Tetrahydrolipstatin\u5173\u952e\u4e2d\u95f4\u4f53\u7684\u5408\u6210(Fig. 2b)\u3002\u6b64\u5916\uff0c\u4f5c\u8005\u8fd8\u6210\u529f\u7684\u5c06\u4e0a\u8ff0\u7684\u7b56\u7565\u5e94\u7528\u4e8e(\u2212)-1-Hydroxypyrrolizidine, (\u2212)-Perhydro-8-indolizinol, (\u2212)-Trachelanthamidine \u4e0e\u00a0(\u2212)-Tashiromine\u7684\u5168\u5408\u6210\u4e2d\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u8be5\u7b56\u7565\u7684\u5b9e\u7528\u6027(Fig. 2c)\u3002\"\"<\/p>\n

\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u5bf9\u4e0a\u8ff0\u53cd\u5e94\u7684\u673a\u7406\u8fdb\u884c\u4e86\u8fdb\u4e00\u6b65\u7814\u7a76\u00a0(Fig. 3)\u3002\u81ea\u7531\u57fa\u6355\u83b7\u5b9e\u9a8c\u7ed3\u679c\u8868\u660e\uff0c\u53d4\u4e01\u6c27\u57fa\u81ea\u7531\u57fa\u4eceC(sp<\/em>3<\/sup>)\u2013H\u5e95\u7269\u4e2d\u652b\u53d6\u4e00\u4e2a\u6c22\u539f\u5b50\uff0c\u5f62\u6210\u4e86\u76f8\u5e94\u7684\u78b3\u4e2d\u5fc3\u81ea\u7531\u57fa(Fig. 3a)\u3002\u540c\u65f6\uff0c\u901a\u8fc7\u70f7\u57fa\u7845\u70f7\u7684\u5bf9\u7167\u5b9e\u9a8c\u7ed3\u679c\uff0c\u6392\u9664\u4e86\u70ef\u70c3\u901a\u8fc7\u6c22\u7845\u5316\u5f62\u6210\u70f7\u57fa\u7845\u70f7\u4f5c\u4e3a\u5173\u952e\u4e2d\u95f4\u4f53\u7684\u53ef\u80fd\u6027(Fig. 3b)\u3002KIE\u5b9e\u9a8c\u7ed3\u679c\u8868\u660e\uff0c\u50ac\u5316\u53cd\u5e94\u4e2d\u7684\u5468\u8f6c\u9650\u901f\u6b65\u9aa4\u53ef\u80fd\u662f\u70f7\u6c27\u81ea\u7531\u57fa\u5bf9C(sp<\/em>3<\/sup>)\u2013H\u952e\u7684\u65ad\u88c2\u200c(Fig. 3c\u4e0eFig. 3d)\u3002\u70f7\u57fa-Ni(II)\u914d\u5408\u726999<\/b><\/strong>\u7684\u5316\u5b66\u8ba1\u91cf\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0c\u70f7\u57fa-Ni(II)\u914d\u5408\u7269\u53ef\u80fd\u662f\u8fd9\u79cd\u8f6c\u5316\u4e2d\u7684\u53cd\u5e94\u6027\u4e2d\u95f4\u4f53(Fig. 3e)\u3002\u5229\u7528\u4e0d\u540c\u7684\u954d\u914d\u5408\u7269\u8fd8\u539fDCP\u7684\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0cL8<\/b><\/strong>Ni(I)Br\u8fd8\u539f\u4e86DCP\uff0c\u5176\u7531Zn\u8fd8\u539fL8<\/b><\/strong>Ni(II)Br2<\/sub>\u751f\u6210(Fig. 3f)\u3002\u70ef\u70c3\u5f02\u6784\u4f53\u6df7\u5408\u7269\u7684\u533a\u57df\u6c47\u805a\u6027\u5b9e\u9a8c\u7ed3\u679c\u8868\u660e\uff0cNi\u2013H\u5bf9\u70ef\u70c3\u7684\u8fc1\u79fb\u63d2\u5165\u8fc7\u7a0b\u4e0d\u5177\u6709\u533a\u57df\u4e13\u4e00\u6027\uff0c\u652f\u94fe\u70f7\u57fa-\u954d\u4e2d\u95f4\u4f53\u4e0e\u5176\u7ebf\u6027\u5f02\u6784\u4f53\u4e4b\u95f4\u901a\u8fc7\u03b2<\/i><\/em>-H\u6d88\u9664\u548c\u70ef\u70c3\u518d\u63d2\u5165\u5b9e\u73b0\u76f8\u4e92\u8f6c\u5316\u662f\u53ef\u884c\u7684\u200c(Fig. 3g)\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 (Fig. 3h)\u3002\u9996\u5148\uff0c\u8fc7\u6c27\u5316\u7269\u6c27\u5316(RO)Ni(I)L*\u914d\u5408\u7269A<\/b><\/strong>\u4f1a\u4ea7\u751f\u70ed\u529b\u5b66\u7a33\u5b9a\u7684L*Ni(II)(OR)2<\/sub>\u4e2d\u95f4\u4f53B<\/b><\/strong>\u548c\u70f7\u6c27\u57fa\u81ea\u7531\u57fa\u3002\u5728\u950c\u7c89\u7684\u5b58\u5728\u4e0b\uff0cNi(II)\u4e2d\u95f4\u4f53B<\/b><\/strong>\u53ef\u8fd8\u539f\u4e3aNi(I)\u914d\u5408\u7269A<\/b><\/strong>\u3002\u5176\u4e2d\uff0cB<\/b><\/strong>\u548cA<\/b><\/strong>\u4e4b\u95f4\u76f8\u4e92\u8f6c\u5316\u53ef\u589e\u52a0\u70f7\u6c27\u57fa\u81ea\u7531\u57fa\u7684\u6d53\u5ea6\uff0c\u4ece\u800c\u63d0\u9ad8HAT\u8fc7\u7a0b\u7684\u6548\u7387\u3002\u5176\u6b21\uff0cNi(II)\u914d\u5408\u7269B<\/b><\/strong>\u4e0e\u7845\u70f7\u53d1\u751f\u8f6c\u91d1\u5c5e\u5316\u53cd\u5e94\uff0c\u751f\u6210\u6c22\u5316\u954d(II)\u914d\u5408\u7269C<\/b><\/strong>\u3002\u5185\u70ef\u70c3\u5728Ni-H\u914d\u5408\u7269\u4e2d\u7684\u5feb\u901f\u8fc1\u79fb\u63d2\u5165\uff0c\u751f\u6210\u70f7\u57fa\u954d(II)\u4e2d\u95f4\u4f53D<\/b><\/strong>\u3002\u7136\u540e\uff0c\u652f\u94fe\u70f7\u57fa-\u954d(II)\u4e2d\u95f4\u4f53D<\/b><\/strong>\u901a\u8fc7\u03b2<\/i><\/em>-H\u6d88\u9664\u548c\u70ef\u70c3\u91cd\u65b0\u63d2\u5165\u7684\u76f8\u4e92\u8f6c\u5316\uff0c\u53ef\u751f\u6210\u76f8\u5e94\u7684\u76f4\u94fe\u5f02\u6784\u4f53E<\/b><\/strong>\u3002\u4ece\u9971\u548c\u6742\u73af\u5316\u5408\u7269\u5230\u70f7\u6c27\u57fa\u81ea\u7531\u57fa\u7684HAT\u751f\u6210\u70f7\u57fa\u81ea\u7531\u57faF<\/b><\/strong>\uff0c\u5176\u53ef\u88ab\u76f4\u94fe\u70f7\u57fa-Ni(II)\u4e2d\u95f4\u4f53E<\/b><\/strong>\u6355\u83b7\uff0c\u751f\u6210Ni(III)\u914d\u5408\u7269G<\/b><\/strong>\u3002Ni(III)\u4e2d\u95f4\u4f53G<\/b><\/strong>\u7ecf\u8fd8\u539f\u6d88\u9664\uff0c\u53ef\u751f\u6210\u6240\u9700\u7684C(sp<\/em>3<\/sup>)\u2013H\u70f7\u57fa\u5316\u4ea7\u7269\uff0c\u5e76\u518d\u751f\u50ac\u5316\u6d3b\u6027(RO)Ni(I)\u914d\u5408\u7269A<\/b><\/strong>\u3002\u6b64\u5916\uff0c\u652f\u94fe\u70f7\u57fa-\u954d\u4e2d\u95f4\u4f53\u8f6c\u5316\u4e3a\u76f4\u94fe\u70f7\u57fa-\u954d\u914d\u5408\u7269\u7684\u9a71\u52a8\u529b\u53ef\u80fd\u662f\u7a7a\u95f4\u4f4d\u963b\uff0c\u81ea\u7531\u57faF<\/b><\/strong>\u4f18\u5148\u653b\u51fb\u76f4\u94fe\u70f7\u57fa-\u954dE<\/b><\/strong>\u5f62\u6210Ni(III)\u4e2d\u95f4\u4f53G<\/b><\/strong>\uff0c\u800c\u4e0d\u662f\u652f\u94fe\u70f7\u57fa-\u954dD<\/b><\/strong>\u5f62\u6210Ni(III)\u4e2d\u95f4\u4f53H<\/b><\/strong>\u3002\u03b1<\/i><\/em>-\u787c\u57fa\u5bfc\u5411\u57fa\u56e2\u53ef\u4ee5\u7a33\u5b9a\u70ef\u57fa\u787c\u9178\u916f\u5e95\u7269\u7ecf\u6c22\u954d\u5316\u751f\u6210\u7684\u652f\u94fe\u6709\u673a\u954d\u4e2d\u95f4\u4f53I<\/b><\/strong>\uff0c\u540c\u65f6\u907f\u514d\u94fe\u884c\u8d70\u83b7\u5f97\u76f4\u94fe\u6709\u673a\u954d\u4e2d\u95f4\u4f53\u3002\u81ea\u7531\u57faF<\/b><\/strong>\u4e0e\u4e2d\u95f4\u4f53I<\/b><\/strong>\u53cd\u5e94\u751f\u6210Ni(III)\u4e2d\u95f4\u4f53J<\/b><\/strong>\uff0c\u7136\u540e\u7ecf\u8fd8\u539f\u6d88\u9664\uff0c\u53ef\u83b7\u5f97\u542b\u6709\u4e24\u4e2a\u8fde\u7eed\u624b\u6027\u4e2d\u5fc3\u7684\u787c\u9178\u70f7\u57fa\u916f\u3002<\/p>\n

\"\"<\/p>\n

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

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