{"id":55385,"date":"2025-04-03T08:00:22","date_gmt":"2025-04-03T00:00:22","guid":{"rendered":"\/\/www.gsbet888.com\/?p=55385"},"modified":"2025-04-03T08:24:04","modified_gmt":"2025-04-03T00:24:04","slug":"jacs%ef%bc%9a%e9%93%9c%e5%82%ac%e5%8c%961122-%e5%9b%9b%e5%8f%96%e4%bb%a3%e4%be%9b%e4%bd%93-%e5%8f%97%e4%bd%93%e7%8e%af%e4%b8%99%e7%83%b7%e7%9a%84%e4%b8%8d%e5%af%b9%e7%a7%b0%e4%ba%b2%e6%a0%b8","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2025\/04\/jacs%ef%bc%9a%e9%93%9c%e5%82%ac%e5%8c%961122-%e5%9b%9b%e5%8f%96%e4%bb%a3%e4%be%9b%e4%bd%93-%e5%8f%97%e4%bd%93%e7%8e%af%e4%b8%99%e7%83%b7%e7%9a%84%e4%b8%8d%e5%af%b9%e7%a7%b0%e4%ba%b2%e6%a0%b8.html","title":{"rendered":"JACS\uff1a\u94dc\u50ac\u53161,1,2,2-\u56db\u53d6\u4ee3\u4f9b\u4f53-\u53d7\u4f53\u73af\u4e19\u70f7\u7684\u4e0d\u5bf9\u79f0\u4eb2\u6838\u5f00\u73af\u53cd\u5e94"},"content":{"rendered":"

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

\u5bfc\u8bfb\uff1a<\/h4>\n
\u8fd1\u65e5\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u798f\u5efa\u7269\u8d28\u7ed3\u6784\u7814\u7a76\u6240\u7684\u623f\u65b0\u5f3a\u7b49\u8bfe\u9898\u7ec4\u5728J. Am. Chem. Soc.<\/em>\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u94dc\u50ac\u53161,1,2,2-\u56db\u53d6\u4ee3\u4f9b\u4f53-\u53d7\u4f53\u73af\u4e19\u70f7(onor\u2212acceptor cyclopropanes, DACs)\u7684\u4e0d\u5bf9\u79f0\u4eb2\u6838\u5f00\u73af\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u624b\u6027\u03b1<\/em>-\u4e09\u7ea7\u80fa\u884d\u751f\u7269\u3002\u540c\u65f6\uff0c\u901a\u8fc7\u540e\u671f\u884d\u751f\u5316\u5b9e\u9a8c\u4ee5\u53ca\u751f\u7269\u6d3b\u6027\u5206\u5b50\u7684\u4e0d\u5bf9\u79f0\u5408\u6210\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002\u673a\u7406\u7814\u7a76\u8868\u660e\uff0c\u542b\u6709copper-acetylide\u5355\u5143\u7684\u4e24\u6027\u79bb\u5b50\u4e2d\u95f4\u4f53\u5728\u8be5\u8fc7\u7a0b\u4e2d\u8d77\u7740\u5173\u952e\u4f5c\u7528\uff0c\u8fd9\u4ee3\u8868\u4e86\u5b9e\u73b0DACs\u50ac\u5316\u4e0d\u5bf9\u79f0\u8f6c\u5316\u7684\u65b0\u6a21\u5f0f\u3002<\/p>\n
\n
Copper-Catalyzed Asymmetric Nucleophilic Opening of 1,1,2,2-Tetrasubstituted Donor\u2212Acceptor Cyclopropanes for the Synthesis of \u03b1\u2011Tertiary Amines<\/p>\n
S. Lan, Q. Cui, D. Luo, S. Shi, C. He, S. Huang, C. Xu, L. Zhao, J. Liu, C. Gu, S. Yang, X. Fang, J. Am. Chem. Soc.<\/em>2024<\/strong>, ASAP. doi: 10.1021\/jacs.4c14944<\/a>.<\/u><\/p><\/blockquote>\n
$\"\"$ <\/p>\n
\u6b63\u6587\uff1a<\/h4>\n
\u5728\u8fc7\u53bb\u5341\u5e74\u4e2d\uff0c\u8bf8\u591a\u7814\u7a76\u7814\u7a76\u56e2\u961f\u5df2\u7ecf\u6210\u529f\u8bbe\u8ba1\u51fa\u591a\u79cdDACs\u53c2\u4e0e\u7684\u50ac\u5316\u4e0d\u5bf9\u79f0\u53cd\u5e94\u3002\u5176\u4e2d\uff0cLewis\u9178\u50ac\u5316DACs\u7684\u4e0d\u5bf9\u79f0\u5f00\u73af\u4e0e\u52a0\u6210\u662f\u4e00\u79cd\u5e38\u7528\u7684\u7b56\u7565^{[1] <\/sup>(Scheme 1a, eq 1)\u3002\u540c\u65f6\uff0c\u5316\u5b66\u5bb6\u4eec\u8fd8\u5f00\u53d1\u4e86\u6709\u673a\u50ac\u5316\u542b\u6709\u919b\u6216\u916e\u5355\u5143\u7684DACs\u53c2\u4e0e\u7684\u4e0d\u5bf9\u79f0\u5f00\u73af\u4e0e\u52a0\u6210\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u73af\u52a0\u6210\u4ea7\u7269^{[2]<\/sup> (Scheme 1a, eq 2)\u3002\u6b64\u5916\uff0cTsuji\u548cTrost\u8bfe\u9898\u7ec4\u9996\u6b21\u91c7\u7528\u4e59\u70ef\u73af\u4e19\u70f7\u4f5c\u4e3aDACs\u7684\u4e00\u4e2a\u91cd\u8981\u4e9a\u7c7b\uff0c\u5e76\u6210\u529f\u5e94\u7528\u4e8e\u5404\u79cd\u5bf9\u6620\u9009\u62e9\u6027\u73af\u5316\u4e0e\u5f00\u73af\u53cd\u5e94^{[3]<\/sup> (Scheme 1a, eq 3)\u3002\u5e76\u4e14\uff0cDACs\u53c2\u4e0e\u7684\u4e0d\u5bf9\u79f0\u81ea\u7531\u57fa\u53cd\u5e94\uff0c\u4f5c\u4e3a\u8fdb\u4e00\u6b65\u6269\u5927\u8fd9\u4e00\u9886\u57df\u7684\u65b0\u7b56\u7565^{[4]<\/sup>\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u7531\u4e8e1,1,2,2-\u56db\u53d6\u4ee3DACs\u53c2\u4e0e\u7684\u53cd\u5e94\u80fd\u591f\u751f\u6210\u5177\u6709\u56db\u53d6\u4ee3\u624b\u6027\u4e2d\u5fc3\u7684\u4ea7\u54c1\uff0c\u8fd9\u4e9b\u4ea7\u7269\u5bf9\u4e8e\u5408\u6210\u76f8\u5173\u590d\u6742\u529f\u80fd\u5206\u5b50\u975e\u5e38\u6709\u4ef7\u503c\u3002\u7136\u800c\uff0c\u5bf9\u4e8e1,1,2,2-\u56db\u53d6\u4ee3DACs\u53c2\u4e0e\u7684\u50ac\u5316\u4e0d\u5bf9\u79f0\u8f6c\u5316\u4ecd\u7136\u662f\u4e00\u4e2a\u672a\u89e3\u51b3\u7684\u6311\u6218 (Scheme 1b)\u3002\u8fd9\u91cc\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u798f\u5efa\u7269\u8d28\u7ed3\u6784\u7814\u7a76\u6240\u7684\u623f\u65b0\u5f3a\u7b49\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u94dc\u50ac\u5316\u56db\u53d6\u4ee3DACs\u7684\u4e0d\u5bf9\u79f0\u4eb2\u6838\u5f00\u73af\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u624b\u6027\u03b1<\/em>-\u4e09\u7ea7\u80fa\u884d\u751f\u7269\uff0c\u5177\u6709\u9ad8\u5ea6\u7684\u5bf9\u6620\u9009\u62e9\u6027\uff0c\u5e76\u4f5c\u4e3a\u4f20\u7edfLewis\u9178\u50ac\u5316\u4f53\u7cfb\u7684\u8865\u5145\u3002\u5176\u4e2d\uff0c\u4e9a\u4e19\u4e8c\u70ef\u57fa\u94dc(copper allenylidene) \u4e2d\u95f4\u4f53I<\/strong>\u4f5c\u4e3a\u53cd\u5e94\u7684\u5173\u952e\u7684\u4e2d\u95f4\u4f53\uff0c\u5176\u5171\u632f\u7ed3\u6784\u4e3a1,3-\u4e24\u6027\u79bb\u5b50\u4e2d\u95f4\u4f53II<\/strong>\uff0c\u8fd9\u79cd\u53cd\u5e94\u6a21\u5f0f\u4ee3\u8868\u4e86\u5b9e\u73b0DACs\u4e0d\u5bf9\u79f0\u53cd\u5e94\u7684\u4e0d\u540c\u65b9\u6cd5(Scheme 1c)\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u4ea7\u7269\u4e2d\u7684\u7094\u57fa\u3001\u6c28\u57fa\u4e0e\u70f7\u6c27\u7fb0\u57fa\u5355\u5143\uff0c\u53ef\u8fdb\u884c\u5404\u79cd\u8f6c\u5316\uff0c\u5982\u542b\u6c2e\u751f\u7269\u6d3b\u6027\u5316\u5408\u7269\u4e0e\u836f\u7269\u5206\u5b50\u7684\u4e0d\u5bf9\u79f0\u5408\u6210\u3002\u4f8b\u5982\uff0c\u4e00\u7cfb\u5217\u03b1<\/em>-\u4e09\u7ea7\u80fa\u3001\u5421\u54af\u70f7\u4e0e\u5421\u54af\u70f7\u916e\u663e\u793a\u51fa\u6709\u524d\u666f\u7684\u751f\u7269\u6d3b\u6027\uff0c\u5982S1P\u6216\u03c3<\/em>-1\u53d7\u4f53\u6fc0\u52a8\u5242\u4e0eanti<\/em>-HIV-1\u7b49(Scheme 1d)\u3002<\/p>\n}}}}
\u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u5916\u6d88\u65cb\u56db\u53d6\u4ee3DAC\u884d\u751f\u72691a<\/strong>\u4e0e\u82ef\u80fa2a<\/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\u7528CuEH\u4f5c\u4e3a\u50ac\u5316\u5242\uff0cL_{13<\/sub><\/strong>\u4f5c\u4e3a\u624b\u6027\u914d\u4f53\uff0cEt_{3<\/sub>N\u4f5c\u4e3a\u78b1\uff0c\u5728CH_{2<\/sub>Cl_{2<\/sub>\u53cd\u5e94\u6eb6\u5242\u4e2d\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a\u5ba4\u6e29\uff0c\u6700\u7ec8\u83b7\u5f9795%\u6536\u7387\u7684\u4ea7\u72693a<\/strong>(95% ee<\/em>)\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u94dc\u6297\u8861\u79bb\u5b50\u5728\u53cd\u5e94\u7684\u5bf9\u6620\u9009\u62e9\u6027\u4e2d\u8d77\u7740\u91cd\u8981\u4f5c\u7528\u3002<\/p>\n}}}}
\u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u5bf9\u4e00\u7cfb\u5217\u5e95\u7269\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76(Scheme 2)\u3002\u9996\u5148\uff0c\u5f53\u4e00\u7ea7\u80fa\u5e95\u7269\u4e2d\u7684R^{2<\/sup>\u4e3a\u4e0d\u540c\u7535\u6027\u53d6\u4ee3\u7684\u82b3\u57fa\u3001\u8418\u57fa\u4e0e\u567b\u5429\u57fa\u65f6\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693a<\/strong>–3m<\/strong>\uff0c\u6536\u7387\u4e3a66-96%\uff0cee\u4e3a88-96%\u3002\u7136\u800c\uff0c\u5bf9\u4e8e\u4e8c\u7ea7\u80fa\uff08\u5982\u5417\u5549\uff09\uff0c\u53ef\u4ee593%\u7684\u6536\u7387\u5f97\u5230\u4ea7\u72693n<\/strong>\uff0c\u4f46\u5bf9\u6620\u9009\u62e9\u6027\u4ec5\u4e3a67%\u3002\u540c\u65f6\uff0c\u8102\u80aa\u65cf\u4e00\u7ea7\u80fa\uff0c\u672a\u80fd\u6709\u6548\u7684\u53c2\u4e0e\u53cd\u5e94\u3002N<\/em>-\u7532\u57fa\u82ef\u80fa\uff0c\u5219\u751f\u6210\u590d\u6742\u7684\u53cd\u5e94\u6df7\u5408\u7269\uff0c\u800c\u975e\u76ee\u6807\u4ea7\u7269\u3002\u5176\u6b21\uff0c\u5f53DACs\u5e95\u7269\u4e2d\u7684R^{1<\/sup>\u4e3a\u4e0d\u540c\u7535\u6027\u53d6\u4ee3\u7684\u82b3\u57fa\u4e0e\u567b\u5429\u57fa\u65f6\uff0c\u4e5f\u80fd\u591f\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693o<\/strong>–3v<\/strong>\uff0c\u6536\u7387\u4e3a86-98%\uff0cee\u4e3a88-95%\u3002\u5f53DAC\u5e95\u7269\u4e2d\u7684R^{1<\/sup>\u542b\u6709\u70ef\u57fa\u65f6\uff0c\u53ef\u4ee582%\u7684\u6536\u7387\u4e0e80%ee\u5f97\u5230\u4ea7\u72693w<\/strong>\u3002\u5f53DAC\u5e95\u7269\u4e2d\u7684R^{1<\/sup>\u4e3a\u7532\u57fa\u65f6\uff0c\u53ef\u4ee540%\u7684\u6536\u7387\u4e0e62%ee\u5f97\u5230\u4ea7\u72693x<\/strong>\u3002\u6b64\u5916\uff0c\u5f53\u540c\u65f6\u6539\u53d8\u5e95\u7269\u4e2d\u7684R^{1<\/sup>\u4e0eR^{2<\/sup>\u65f6\uff0c\u4e5f\u80fd\u591f\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693aa<\/strong>–3ag<\/strong>\uff0c\u6536\u7387\u4e3a86-97%\uff0cee\u4e3a82-95%\u30024-\u7532\u6c27\u57fa\u82ef\u80fa\u8fd8\u53ef\u4e0e\u51e0\u79cd\u82b3\u57fa\u6216\u4e59\u70ef\u57fa\u53d6\u4ee3\u7684DACs\u53cd\u5e94\uff0c\u5f97\u76f8\u5e94\u7684\u4ea7\u72693ah<\/strong>–3al<\/strong>\uff0c\u6536\u7387\u4e3a83-93%\uff0cee\u4e3a80-95%\u3002<\/p>\n}}}}}}
\u7d27\u63a5\u7740\uff0c\u4f5c\u8005\u5bf9\u5929\u7136\u4ea7\u7269\u6216\u836f\u7269\u5206\u5b50\u7684\u540e\u671f\u884d\u751f\u5316\u8fdb\u884c\u4e86\u7814\u7a76(Scheme 3)\u3002\u7814\u7a76\u7ed3\u679c\u8868\u660e\uff0c\u542b\u6709\u6c28\u57fa\u9999\u8c46\u7d20\u3001\u7d2b\u6a80\u82aa\u3001\u666e\u9c81\u5361\u56e0\u4e0eL<\/em>-\u8584\u8377\u9187\u7684\u5e95\u7269\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u5f97\u76f8\u5e94\u7684\u4ea7\u72693am<\/strong>–3ap<\/strong>\uff0c\u6536\u7387\u4e3a51-90%\uff0cee\u4e3a89-93%\u3002 $\"\"$ <\/p>\n
\u540c\u65f6\uff0c1a<\/strong>\u4e0e2b<\/strong>\u7684\u514b\u7ea7\u89c4\u6a21\u5b9e\u9a8c\uff0c\u540c\u6837\u53ef\u4ee596%\u7684\u6536\u7387\u4e0e95%ee\u5f97\u5230\u4ea7\u72693b<\/strong> (Scheme 4a)\u30023h<\/strong>\u7ecf\u91d1\u50ac\u5316\u7684\u73af\u5316\u4e0e\u5185\u9170\u80fa\u5316\u53cd\u5e94\uff0c\u53ef\u4ee587%\u7684\u6536\u7387\u5f97\u5230\u5316\u5408\u72694a<\/strong>\uff0cee\u4e3a98%\uff0cdr\u4e3a4:1(Scheme 4b)\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u901a\u8fc7\u785d\u9178\u94c8\u94f5(CAN)-\u4ecb\u5bfc\u7684\u8131PMP\u4fdd\u62a4\u57fa\u56e2\u4ee5\u53caNaHCO_{3<\/sub>-\u4fc3\u8fdb\u7684\u73af\u5316\uff0c\u53ef\u751f\u6210\u5185\u9170\u80fa\u5316\u5408\u7269\uff0c\u5176\u53ef\u4e0e\u4e0d\u540c\u7684\u4eb2\u7535\u8bd5\u5242\u8fdb\u884c\u8fdb\u4e00\u6b65\u7684\u53cd\u5e94\uff0c\u4ece\u800c\u83b7\u5f97\u5177\u6709\u4e24\u4e2a\u4e0d\u76f8\u90bb\u7684\u5b63\u78b3\u624b\u6027\u4e2d\u5fc3\u7684\u5316\u5408\u7269\uff0c\u59825a<\/strong>–5d<\/strong>(Scheme 4c)\u3002<\/p>\n}
\u6b64\u5916\uff0c\u5229\u7528\u8be5\u7b56\u7565\u8fd8\u53ef\u5b9e\u73b0\u76f8\u5173\u751f\u7269\u6d3b\u6027\u5206\u5b50\u7684\u4e0d\u5bf9\u79f0\u5408\u6210(Scheme 5)\u3002\u4ee53b<\/strong>\u4e3a\u521d\u59cb\u5e95\u7269\uff0c\u7ecfCAN-\u4ecb\u5bfc\u7684\u8131PMP\u4fdd\u62a4\u57fa\u56e2\u3001NaHCO_{3<\/sub>-\u4fc3\u8fdb\u7684\u73af\u5316\u3001\u8131\u7fa7\u4e0e\u6c22\u5316\u53cd\u5e94\uff0c\u53ef\u83b7\u5f97\u5316\u5408\u72696b<\/strong>(94%ee)\uff0c\u5176\u662f\u4e00\u79cd\u6f5c\u5728\u7684\u9547\u9759\u50ac\u7720\u5242(Scheme 5a)\u3002\u4ee53b<\/strong>\u4e3a\u521d\u59cb\u5e95\u7269\uff0c\u7ecf\u8131\u7fa7\u3001\u78b1\u4ecb\u5bfc\u7684\u73af\u5316\u3001\u7fb0\u57fa\u7684\u8fd8\u539f\u3001CAN-\u4ecb\u5bfc\u7684\u8131PMP\u4fdd\u62a4\u57fa\u56e2\/\u6c28\u57fa\u7684Boc\u4fdd\u62a4\u3001\u7094\u57fa\u7684\u6c22\u5316\u3001\u70ef\u57fa\u7684\u53cc\u7f9f\u57fa\u5316\u3001\u4f7f\u7528NaIO_{4<\/sub>\u6c27\u5316\u4e8c\u9187\u751f\u6210\u919b\u4ee5\u53ca\u968f\u540e\u7532\u9170\u57fa\u7684\u8fd8\u539f\u3001\u7f9f\u57fa\u7684\u70f7\u57fa\u5316\u4ee5\u53caBoc\u7684\u8131\u4fdd\u62a4\u53cd\u5e94\uff0c\u53ef\u83b7\u5f97\u5316\u5408\u72697i<\/strong>(96%ee)\uff0c\u5176\u662f\u4e00\u79cdtachykinin\u62ee\u6297\u5242\uff0c\u5e76\u4e14\u4f5c\u4e3a\u9996\u4e2a\u76f8\u5173\u7684\u624b\u6027\u5206\u5b50(Scheme 5b)\u3002\u4ee53ab<\/strong>\u4e3a\u521d\u59cb\u5e95\u7269\uff0c\u7ecf\u8131\u7fa7\u3001\u78b1\u4ecb\u5bfc\u7684\u73af\u5316\u3001\u7f9f\u57fa\u7684\u8fd8\u539f\u3001CAN-\u4ecb\u5bfc\u7684\u8131PMP\u4fdd\u62a4\u57fa\u56e2\/\u6c28\u57fa\u7684Boc\u4fdd\u62a4\u4ee5\u53ca\u7094\u57fa\u7684\u6c22\u5316\u53cd\u5e94\uff0c\u53ef\u83b7\u5f97\u5316\u5408\u72698e<\/strong>(98%ee)\uff0c\u5176\u4f5c\u4e3a\u4e00\u79cd\u6cbb\u7597\u57fa\u4e8e\u03b2<\/em>-catenin\u7684\u75be\u75c5\uff0c\u4e5f\u662f\u4e00\u79cd\u5f3a\u5927\u7684\u9ed1\u8272\u7d20\u76ae\u8d284\u53d7\u4f53\uff08MC4R\uff09\uff0c\u5e76\u4e14\u4e5f\u4f5c\u4e3a\u9996\u4e2a\u76f8\u5173\u7684\u624b\u6027\u5206\u5b50(Scheme 5c)\u3002<\/p>\n}}
\u968f\u540e\uff0c\u4f5c\u8005\u5bf9\u53cd\u5e94\u7684\u673a\u7406\u8fdb\u884c\u4e86\u7814\u7a76(Scheme 6)\u3002\u9996\u5148\uff0c1a-Ph<\/strong>\u62161a-TMS<\/strong>\u5206\u522b\u4e0e2a<\/strong>\u7684\u5bf9\u7167\u5b9e\u9a8c\u7ed3\u679c\u8868\u660e\uff0c\u672b\u7aef\u7094\u57fa\u5355\u5143\u5bf9\u4e8e\u53cd\u5e94\u7684\u5177\u6709\u91cd\u8981\u6027\u30021a-D<\/strong>\u4e0e2a<\/strong>\u7684\u6c18\u4ee3\u5b9e\u9a8c\u7ed3\u679c\u8868\u660e\uff0c\u672b\u7aef\u7094\u57fa\u5355\u5143\u53ef\u80fd\u53c2\u4e0e\u4e86\u53cd\u5e94(Scheme 6a)\u3002\u5176\u6b21\uff0c\u4f7f\u7528\u5177\u6709\u4e0d\u540cee\u503c\u7684\u914d\u4f53L_{13<\/sub><\/strong>\u7684\u7814\u7a76\u8868\u660e\uff0c\u94dc\u914d\u4f53\u5355\u4f53\u662f\u4e00\u79cd\u53ef\u80fd\u7684\u6d3b\u6027\u50ac\u5316\u7269\u79cd(Scheme 6b)\u3002\u52a8\u529b\u5b66\u7814\u7a76\u8868\u660e\uff0c\u94dc\u50ac\u5316\u73af\u5f00\u653e\u548c\u6c28\u57fa\u4ecb\u5bfc\u7684\u4eb2\u6838\u8fdb\u653b\u6d89\u53ca\u901f\u5ea6\u51b3\u5b9a\u6b65\u9aa4(Scheme 6c)\u3002\u6b64\u5916\uff0c\u91c7\u7528\u4e0d\u540c\u7684Lewis\u9178\u7684\u5bf9\u7167\u5b9e\u9a8c\uff0c\u8fdb\u4e00\u6b65\u8868\u660e\u4e86\u8fd9\u79cd\u65b0\u578b\u7acb\u4f53\u9009\u62e9\u6027\u8bf1\u5bfc\u6a21\u578b\u7684\u4f18\u52bf(Scheme 6d)\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 7a)\u3002\u9996\u5148\uff0cCu^{II<\/sup>-\u914d\u4f53\u914d\u5408\u7269\u53ef\u80fd\u88ab\u4e09\u7ea7\u80fa\u6216\u82ef\u80fa\u8fd8\u539f\uff0c\u751f\u6210Cu^{I<\/sup>\u914d\u5408\u7269\u3002\u5176\u6b21\uff0cCu^{I<\/sup>\u914d\u5408\u7269\u4e0e1a<\/strong>\u7684\u53cd\u5e94\u751f\u6210\u4e2d\u95f4\u4f53int-I<\/strong>\u3002\u4e2d\u95f4\u4f53int-I<\/strong>\u7ecf\u5f00\u73af\uff0c\u751f\u6210\u4e24\u6027\u79bb\u5b50int-II<\/strong>\uff0c\u5176\u5171\u632f\u7ed3\u6784\u4e3aint-II’<\/strong>\u3002\u968f\u540e\uff0c\u82ef\u80fa\u4ee5\u5bf9\u6620\u9009\u62e9\u6027\u7684\u65b9\u5f0f\u8fdb\u653bint-II<\/strong>\uff0c\u751f\u6210\u4e2d\u95f4\u4f53int-III<\/strong>\u3002\u6700\u540e\uff0cint-III<\/strong>\u7ecf\u8d28\u5b50\u5316\u540e\uff0c\u4ece\u800c\u83b7\u5f97\u76ee\u6807\u4ea7\u72693a<\/strong>\u3002\u6b64\u5916\uff0c\u4f5c\u8005\u8fd8\u63d0\u51fa\u4e86\u4e24\u79cd\u53ef\u80fd\u7684\u8fc7\u6e21\u6001\uff0c\u7528\u4e8e\u5bf9\u6620\u9009\u62e9\u6027\u8d77\u6e90\u7684\u7814\u7a76(Scheme 7b)\u3002\u5176\u4e2d\uff0cTS-I<\/strong>\u5177\u6709\u7a7a\u95f4\u4f18\u52bf\uff0c\u6709\u5229\u4e8e\u5f62\u6210(S<\/em>)-3a<\/strong>\u3002\u76f8\u6bd4\u4e4b\u4e0b\uff0cTS-II<\/strong>\u4e0d\u5229\u4e8e\u751f\u6210(R<\/em>)-3a<\/strong>\uff0c\u53ef\u80fd\u662f\u7531\u4e8e\u914d\u4f53\u4e2d\u7684\u5f02\u4e19\u57fa\u4e0e\u70f7\u6c27\u7fb0\u57fa\u4e4b\u95f4\u7684\u7a7a\u95f4\u4f4d\u963b\u3002<\/p>\n}}}
\u603b\u7ed3\uff1a<\/h4>\n
\u4e2d\u56fd\u79d1\u5b66\u9662\u798f\u5efa\u7269\u8d28\u7ed3\u6784\u7814\u7a76\u6240\u7684\u623f\u65b0\u5f3a\u7b49\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u94dc\u50ac\u53161,1,2,2-\u56db\u53d6\u4ee3\u4f9b\u4f53-\u53d7\u4f53\u73af\u4e19\u70f7\u7684\u4e0d\u5bf9\u79f0\u4eb2\u6838\u5f00\u73af\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u624b\u6027\u03b1<\/em>-\u4e09\u7ea7\u80fa\u884d\u751f\u7269\uff0c\u5177\u6709\u826f\u597d\u81f3\u4f18\u5f02\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0ccopper-acetylide\u4e2d\u95f4\u4f53\u5728\u5b9e\u73b0\u8f6c\u5316\u4e2d\u8d77\u7740\u81f3\u5173\u91cd\u8981\u7684\u4f5c\u7528\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u540e\u671f\u884d\u751f\u5316\u5b9e\u9a8c\u4ee5\u53ca\u76f8\u5173\u751f\u7269\u6d3b\u6027\u5206\u5b50\u7684\u4e0d\u5bf9\u79f0\u5408\u6210\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002\u00a0<\/strong><\/p>\n
\u53c2\u8003\u6587\u732e\uff1a<\/strong><\/h4>\n\n
[1] D. Perrotta, M. M. Wang, J. Waser, Angew. Chem., Int. Ed. <\/em>2018<\/strong>, *57<\/em>, 5120. doi:**10.1002\/anie.201800494<\/a>.<\/li>\n*
[2] L. Candish, C. M. Forsyth, D. W. Lupton, Angew. Chem., Int. Ed. <\/em>2013<\/strong>, *52<\/em>, 9149. doi:**10.1002\/anie.201304081<\/a>.<\/li>\n*
[3] S. J. Webster, L. B. Balazs, F. W. Goetzke, V. Stojalnikova, K. Liu, K. E. Christensen, H. W. Mackenzie, S. P. Fletcher, J. Am. Chem. Soc. <\/em>2024<\/strong>, *146<\/em>, 24708. doi:**10.1021\/jacs.4c09490<\/a>.<\/li>\n*
[4] W. Hao, J. H. Harenberg, X. Wu, S. N. MacMillan, S. Lin, J. Am. Chem. Soc. <\/em>2018<\/strong>, 140<\/em>, 3514. doi:10.1021\/jacs.7b13710<\/a>.<\/li>\n<\/ul>\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","protected":false},"excerpt":{"rendered":"\u4f5c\u8005\uff1a\u6749\u6749 \u5bfc\u8bfb\uff1a \u8fd1\u65e5\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u798f\u5efa\u7269\u8d28\u7ed3\u6784\u7814\u7a76\u6240\u7684\u623f\u65b0\u5f3a\u7b49\u8bfe\u9898\u7ec4\u5728J. Am. Chem. Soc.\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u94dc\u50ac\u53161,1,2,2-\u56db\u53d6\u4ee3\u4f9b\u4f53-\u53d7\u4f53\u73af\u4e19\u70f7(onor\u2212acceptor cyclopropanes, DACs)\u7684\u4e0d\u5bf9\u79f0\u4eb2\u6838\u5f00\u73af\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u624b\u6027\u03b1-\u4e09\u7ea7\u80fa\u884d\u751f\u7269\u3002\u540c\u65f6\uff0c\u901a\u8fc7\u540e\u671f\u884d\u751f\u5316\u5b9e\u9a8c\u4ee5\u53ca\u751f\u7269\u6d3b\u6027\u5206\u5b50\u7684\u4e0d\u5bf9\u79f0\u5408\u6210\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002\u673a\u7406\u7814\u7a76\u8868\u660e\uff0c\u542b\u6709copper-acetylide\u5355\u5143\u7684\u4e24\u6027\u79bb\u5b50\u4e2d\u95f4\u4f53\u5728\u8be5\u8fc7\u7a0b\u4e2d\u8d77\u7740\u5173\u952e\u4f5c\u7528\uff0c\u8fd9\u4ee3\u8868\u4e86\u5b9e\u73b0DACs\u50ac\u5316\u4e0d\u5bf9\u79f0\u8f6c\u5316\u7684\u65b0\u6a21\u5f0f\u3002 Copper-Catalyzed Asymmetric Nucleophilic Opening of 1,1,2,2-Tetrasubstituted Donor\u2212Acceptor Cyclopropanes for the Synthesis of \u03b1\u2011Tertiary Amines S. Lan, Q. Cui, D. Luo, S. Shi, C. He, S. Huang, C. Xu, L. Zhao, J. Liu, C. Gu, S. Yang, X. Fang, J. Am. Chem. Soc.2024, ASAP. doi: 10.1021\/jacs.4c14944. \u6b63\u6587\uff1a \u5728\u8fc7\u53bb\u5341\u5e74\u4e2d\uff0c\u8bf8\u591a\u7814\u7a76\u7814\u7a76\u56e2\u961f\u5df2\u7ecf\u6210\u529f\u8bbe\u8ba1\u51fa\u591a\u79cdDACs\u53c2\u4e0e\u7684\u50ac\u5316\u4e0d\u5bf9\u79f0\u53cd\u5e94\u3002\u5176\u4e2d\uff0cLewis\u9178\u50ac\u5316DACs\u7684\u4e0d\u5bf9\u79f0\u5f00\u73af\u4e0e\u52a0\u6210\u662f\u4e00\u79cd\u5e38\u7528\u7684\u7b56\u7565[1] (Scheme 1a, eq 1)\u3002\u540c\u65f6\uff0c\u5316\u5b66\u5bb6\u4eec\u8fd8\u5f00\u53d1\u4e86\u6709\u673a\u50ac\u5316\u542b\u6709\u919b\u6216\u916e\u5355\u5143\u7684DACs\u53c2\u4e0e\u7684\u4e0d\u5bf9\u79f0\u5f00\u73af\u4e0e\u52a0\u6210\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u73af\u52a0\u6210\u4ea7\u7269[2] (Scheme 1a, eq 2)\u3002\u6b64\u5916\uff0cTsuji\u548cTrost\u8bfe\u9898\u7ec4\u9996\u6b21\u91c7\u7528\u4e59\u70ef\u73af\u4e19\u70f7\u4f5c\u4e3aDACs\u7684\u4e00\u4e2a\u91cd\u8981\u4e9a\u7c7b\uff0c\u5e76\u6210\u529f\u5e94\u7528\u4e8e\u5404\u79cd\u5bf9\u6620\u9009\u62e9\u6027\u73af\u5316\u4e0e\u5f00\u73af\u53cd\u5e94[3] (Scheme 1a, eq 3)\u3002\u5e76\u4e14\uff0cDACs\u53c2\u4e0e\u7684\u4e0d\u5bf9\u79f0\u81ea\u7531\u57fa\u53cd\u5e94\uff0c\u4f5c\u4e3a\u8fdb\u4e00\u6b65\u6269\u5927\u8fd9\u4e00\u9886\u57df\u7684\u65b0\u7b56\u7565[4]\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u7531\u4e8e1,1,2,2-\u56db\u53d6\u4ee3DACs\u53c2\u4e0e\u7684\u53cd\u5e94\u80fd\u591f\u751f\u6210\u5177\u6709\u56db\u53d6\u4ee3\u624b\u6027\u4e2d\u5fc3\u7684\u4ea7\u54c1\uff0c\u8fd9\u4e9b\u4ea7\u7269\u5bf9\u4e8e\u5408\u6210\u76f8\u5173\u590d\u6742\u529f\u80fd\u5206\u5b50\u975e\u5e38\u6709\u4ef7\u503c\u3002\u7136\u800c\uff0c\u5bf9\u4e8e1,1,2,2-\u56db\u53d6\u4ee3DACs\u53c2\u4e0e\u7684\u50ac\u5316\u4e0d\u5bf9\u79f0\u8f6c\u5316\u4ecd\u7136\u662f\u4e00\u4e2a\u672a\u89e3\u51b3\u7684\u6311\u6218 (Scheme 1b)\u3002\u8fd9\u91cc\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u798f\u5efa\u7269\u8d28\u7ed3\u6784\u7814\u7a76\u6240\u7684\u623f\u65b0\u5f3a\u7b49\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u94dc\u50ac\u5316\u56db\u53d6\u4ee3DACs\u7684\u4e0d\u5bf9\u79f0\u4eb2\u6838\u5f00\u73af\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u624b\u6027\u03b1-\u4e09\u7ea7\u80fa\u884d\u751f\u7269\uff0c\u5177\u6709\u9ad8\u5ea6\u7684\u5bf9\u6620\u9009\u62e9\u6027\uff0c\u5e76\u4f5c\u4e3a\u4f20\u7edfLewis\u9178\u50ac\u5316\u4f53\u7cfb\u7684\u8865\u5145\u3002\u5176\u4e2d\uff0c\u4e9a\u4e19\u4e8c\u70ef\u57fa\u94dc(copper allenylidene) \u4e2d\u95f4\u4f53I\u4f5c\u4e3a\u53cd\u5e94\u7684\u5173\u952e\u7684\u4e2d\u95f4\u4f53\uff0c\u5176\u5171\u632f\u7ed3\u6784\u4e3a1,3-\u4e24\u6027\u79bb\u5b50\u4e2d\u95f4\u4f53II\uff0c\u8fd9\u79cd\u53cd\u5e94\u6a21\u5f0f\u4ee3\u8868\u4e86\u5b9e\u73b0DACs\u4e0d\u5bf9\u79f0\u53cd\u5e94\u7684\u4e0d\u540c\u65b9\u6cd5(Scheme 1c)\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u4ea7\u7269\u4e2d\u7684\u7094\u57fa\u3001\u6c28\u57fa\u4e0e\u70f7\u6c27\u7fb0\u57fa\u5355\u5143\uff0c\u53ef\u8fdb\u884c\u5404\u79cd\u8f6c\u5316\uff0c\u5982\u542b\u6c2e\u751f\u7269\u6d3b\u6027\u5316\u5408\u7269\u4e0e\u836f\u7269\u5206\u5b50\u7684\u4e0d\u5bf9\u79f0\u5408\u6210\u3002\u4f8b\u5982\uff0c\u4e00\u7cfb\u5217\u03b1-\u4e09\u7ea7\u80fa\u3001\u5421\u54af\u70f7\u4e0e\u5421\u54af\u70f7\u916e\u663e\u793a\u51fa\u6709\u524d\u666f\u7684\u751f\u7269\u6d3b\u6027\uff0c\u5982S1P\u6216\u03c3-1\u53d7\u4f53\u6fc0\u52a8\u5242\u4e0eanti-HIV-1\u7b49(Scheme 1d)\u3002 \u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u5916\u6d88\u65cb\u56db\u53d6\u4ee3DAC\u884d\u751f\u72691a\u4e0e\u82ef\u80fa2a\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\u7528CuEH\u4f5c\u4e3a\u50ac\u5316\u5242\uff0cL13\u4f5c\u4e3a\u624b\u6027\u914d\u4f53\uff0cEt3N\u4f5c\u4e3a\u78b1\uff0c\u5728CH2Cl2\u53cd\u5e94\u6eb6\u5242\u4e2d\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a\u5ba4\u6e29\uff0c\u6700\u7ec8\u83b7\u5f9795%\u6536\u7387\u7684\u4ea7\u72693a(95% ee)\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u94dc\u6297\u8861\u79bb\u5b50\u5728\u53cd\u5e94\u7684\u5bf9\u6620\u9009\u62e9\u6027\u4e2d\u8d77\u7740\u91cd\u8981\u4f5c\u7528\u3002 \u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u5bf9\u4e00\u7cfb\u5217\u5e95\u7269\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76(Scheme 2)\u3002\u9996\u5148\uff0c\u5f53\u4e00\u7ea7\u80fa\u5e95\u7269\u4e2d\u7684R2\u4e3a\u4e0d\u540c\u7535\u6027\u53d6\u4ee3\u7684\u82b3\u57fa\u3001\u8418\u57fa\u4e0e\u567b\u5429\u57fa\u65f6\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693a–3m\uff0c\u6536\u7387\u4e3a66-96%\uff0cee\u4e3a88-96%\u3002\u7136\u800c\uff0c\u5bf9\u4e8e\u4e8c\u7ea7\u80fa\uff08\u5982\u5417\u5549\uff09\uff0c\u53ef\u4ee593%\u7684\u6536\u7387\u5f97\u5230\u4ea7\u72693n\uff0c\u4f46\u5bf9\u6620\u9009\u62e9\u6027\u4ec5\u4e3a67%\u3002\u540c\u65f6\uff0c\u8102\u80aa\u65cf\u4e00\u7ea7\u80fa\uff0c\u672a\u80fd\u6709\u6548\u7684\u53c2\u4e0e\u53cd\u5e94\u3002N-\u7532\u57fa\u82ef\u80fa\uff0c\u5219\u751f\u6210\u590d\u6742\u7684\u53cd\u5e94\u6df7\u5408\u7269\uff0c\u800c\u975e\u76ee\u6807\u4ea7\u7269\u3002\u5176\u6b21\uff0c\u5f53DACs\u5e95\u7269\u4e2d\u7684R1\u4e3a\u4e0d\u540c\u7535\u6027\u53d6\u4ee3\u7684\u82b3\u57fa\u4e0e\u567b\u5429\u57fa\u65f6\uff0c\u4e5f\u80fd\u591f\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693o–3v\uff0c\u6536\u7387\u4e3a86-98%\uff0cee\u4e3a88-95%\u3002\u5f53DAC\u5e95\u7269\u4e2d\u7684R1\u542b\u6709\u70ef\u57fa\u65f6\uff0c\u53ef\u4ee582%\u7684\u6536\u7387\u4e0e80%ee\u5f97\u5230\u4ea7\u72693w\u3002\u5f53DAC\u5e95\u7269\u4e2d\u7684R1\u4e3a\u7532\u57fa\u65f6\uff0c\u53ef\u4ee540%\u7684\u6536\u7387\u4e0e62%ee\u5f97\u5230\u4ea7\u72693x\u3002\u6b64\u5916\uff0c\u5f53\u540c\u65f6\u6539\u53d8\u5e95\u7269\u4e2d\u7684R1\u4e0eR2\u65f6\uff0c\u4e5f\u80fd\u591f\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693aa–3ag\uff0c\u6536\u7387\u4e3a86-97%\uff0cee\u4e3a82-95%\u30024-\u7532\u6c27\u57fa\u82ef\u80fa\u8fd8\u53ef\u4e0e\u51e0\u79cd\u82b3\u57fa\u6216\u4e59\u70ef\u57fa\u53d6\u4ee3\u7684DACs\u53cd\u5e94\uff0c\u5f97\u76f8\u5e94\u7684\u4ea7\u72693ah–3al\uff0c\u6536\u7387\u4e3a83-93%\uff0cee\u4e3a80-95%\u3002 \u7d27\u63a5\u7740\uff0c\u4f5c\u8005\u5bf9\u5929\u7136\u4ea7\u7269\u6216\u836f\u7269\u5206\u5b50\u7684\u540e\u671f\u884d\u751f\u5316\u8fdb\u884c\u4e86\u7814\u7a76(Scheme 3)\u3002\u7814\u7a76\u7ed3\u679c\u8868\u660e\uff0c\u542b\u6709\u6c28\u57fa\u9999\u8c46\u7d20\u3001\u7d2b\u6a80\u82aa\u3001\u666e\u9c81\u5361\u56e0\u4e0eL-\u8584\u8377\u9187\u7684\u5e95\u7269\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u5f97\u76f8\u5e94\u7684\u4ea7\u72693am–3ap\uff0c\u6536\u7387\u4e3a51-90%\uff0cee\u4e3a89-93%\u3002 \u540c\u65f6\uff0c1a\u4e0e2b\u7684\u514b\u7ea7\u89c4\u6a21\u5b9e\u9a8c\uff0c\u540c\u6837\u53ef\u4ee596%\u7684\u6536\u7387\u4e0e95%ee\u5f97\u5230\u4ea7\u72693b (Scheme 4a)\u30023h\u7ecf\u91d1\u50ac\u5316\u7684\u73af\u5316\u4e0e\u5185\u9170\u80fa\u5316\u53cd\u5e94\uff0c\u53ef\u4ee587%\u7684\u6536\u7387\u5f97\u5230\u5316\u5408\u72694a\uff0cee\u4e3a98%\uff0cdr\u4e3a4:1(Scheme 4b)\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u901a\u8fc7\u785d\u9178\u94c8\u94f5(CAN)-\u4ecb\u5bfc\u7684\u8131PMP\u4fdd\u62a4\u57fa\u56e2\u4ee5\u53caNaHCO3-\u4fc3\u8fdb\u7684\u73af\u5316\uff0c\u53ef\u751f\u6210\u5185\u9170\u80fa\u5316\u5408\u7269\uff0c\u5176\u53ef\u4e0e\u4e0d\u540c\u7684\u4eb2\u7535\u8bd5\u5242\u8fdb\u884c\u8fdb\u4e00\u6b65\u7684\u53cd\u5e94\uff0c\u4ece\u800c\u83b7\u5f97\u5177\u6709\u4e24\u4e2a\u4e0d\u76f8\u90bb\u7684\u5b63\u78b3\u624b\u6027\u4e2d\u5fc3\u7684\u5316\u5408\u7269\uff0c\u59825a–5d(Scheme 4c)\u3002 \u6b64\u5916\uff0c\u5229\u7528\u8be5\u7b56\u7565\u8fd8\u53ef\u5b9e\u73b0\u76f8\u5173\u751f\u7269\u6d3b\u6027\u5206\u5b50\u7684\u4e0d\u5bf9\u79f0\u5408\u6210(Scheme 5)\u3002\u4ee53b\u4e3a\u521d\u59cb\u5e95\u7269\uff0c\u7ecfCAN-\u4ecb\u5bfc\u7684\u8131PMP\u4fdd\u62a4\u57fa\u56e2\u3001NaHCO3-\u4fc3\u8fdb\u7684\u73af\u5316\u3001\u8131\u7fa7\u4e0e\u6c22\u5316\u53cd\u5e94\uff0c\u53ef\u83b7\u5f97\u5316\u5408\u72696b(94%ee)\uff0c\u5176\u662f\u4e00\u79cd\u6f5c\u5728\u7684\u9547\u9759\u50ac\u7720\u5242(Scheme 5a)\u3002\u4ee53b\u4e3a\u521d\u59cb\u5e95\u7269\uff0c\u7ecf\u8131\u7fa7\u3001\u78b1\u4ecb\u5bfc\u7684\u73af\u5316\u3001\u7fb0\u57fa\u7684\u8fd8\u539f\u3001CAN-\u4ecb\u5bfc\u7684\u8131PMP\u4fdd\u62a4\u57fa\u56e2\/\u6c28\u57fa\u7684Boc\u4fdd\u62a4\u3001\u7094\u57fa\u7684\u6c22\u5316\u3001\u70ef\u57fa\u7684\u53cc\u7f9f\u57fa\u5316\u3001\u4f7f\u7528NaIO4\u6c27\u5316\u4e8c\u9187\u751f\u6210\u919b\u4ee5\u53ca\u968f\u540e\u7532\u9170\u57fa\u7684\u8fd8\u539f\u3001\u7f9f\u57fa\u7684\u70f7\u57fa\u5316\u4ee5\u53caBoc\u7684\u8131\u4fdd\u62a4\u53cd\u5e94\uff0c\u53ef\u83b7\u5f97\u5316\u5408\u72697i(96%ee)\uff0c\u5176\u662f\u4e00\u79cdtachykinin\u62ee\u6297\u5242\uff0c\u5e76\u4e14\u4f5c\u4e3a\u9996\u4e2a\u76f8\u5173\u7684\u624b\u6027\u5206\u5b50(Scheme 5b)\u3002\u4ee53ab\u4e3a\u521d\u59cb\u5e95\u7269\uff0c\u7ecf\u8131\u7fa7\u3001\u78b1\u4ecb\u5bfc\u7684\u73af\u5316\u3001\u7f9f\u57fa\u7684\u8fd8\u539f\u3001CAN-\u4ecb\u5bfc\u7684\u8131PMP\u4fdd\u62a4\u57fa\u56e2\/\u6c28\u57fa\u7684Boc\u4fdd\u62a4\u4ee5\u53ca\u7094\u57fa\u7684\u6c22\u5316\u53cd\u5e94\uff0c\u53ef\u83b7\u5f97\u5316\u5408\u72698e(98%ee)\uff0c\u5176\u4f5c\u4e3a\u4e00\u79cd\u6cbb\u7597\u57fa\u4e8e\u03b2-catenin\u7684\u75be\u75c5\uff0c\u4e5f\u662f\u4e00\u79cd\u5f3a\u5927\u7684\u9ed1\u8272\u7d20\u76ae\u8d284\u53d7\u4f53\uff08MC4R\uff09\uff0c\u5e76\u4e14\u4e5f\u4f5c\u4e3a\u9996\u4e2a\u76f8\u5173\u7684\u624b\u6027\u5206\u5b50(Scheme 5c)\u3002 \u968f\u540e\uff0c\u4f5c\u8005\u5bf9\u53cd\u5e94\u7684\u673a\u7406\u8fdb\u884c\u4e86\u7814\u7a76(Scheme 6)\u3002\u9996\u5148\uff0c1a-Ph\u62161a-TMS\u5206\u522b\u4e0e2a\u7684\u5bf9\u7167\u5b9e\u9a8c\u7ed3\u679c\u8868\u660e\uff0c\u672b\u7aef\u7094\u57fa\u5355\u5143\u5bf9\u4e8e\u53cd\u5e94\u7684\u5177\u6709\u91cd\u8981\u6027\u30021a-D\u4e0e2a\u7684\u6c18\u4ee3\u5b9e\u9a8c\u7ed3\u679c\u8868\u660e\uff0c\u672b\u7aef\u7094\u57fa\u5355\u5143\u53ef\u80fd\u53c2\u4e0e\u4e86\u53cd\u5e94(Scheme 6a)\u3002\u5176\u6b21\uff0c\u4f7f\u7528\u5177\u6709\u4e0d\u540cee\u503c\u7684\u914d\u4f53L13\u7684\u7814\u7a76\u8868\u660e\uff0c\u94dc\u914d\u4f53\u5355\u4f53\u662f\u4e00\u79cd\u53ef\u80fd\u7684\u6d3b\u6027\u50ac\u5316\u7269\u79cd(Scheme 6b)\u3002\u52a8\u529b\u5b66\u7814\u7a76\u8868\u660e\uff0c\u94dc\u50ac\u5316\u73af\u5f00\u653e\u548c\u6c28\u57fa\u4ecb\u5bfc\u7684\u4eb2\u6838\u8fdb\u653b\u6d89\u53ca\u901f\u5ea6\u51b3\u5b9a\u6b65\u9aa4(Scheme 6c)\u3002\u6b64\u5916\uff0c\u91c7\u7528\u4e0d\u540c\u7684Lewis\u9178\u7684\u5bf9\u7167\u5b9e\u9a8c\uff0c\u8fdb\u4e00\u6b65\u8868\u660e\u4e86\u8fd9\u79cd\u65b0\u578b\u7acb\u4f53\u9009\u62e9\u6027\u8bf1\u5bfc\u6a21\u578b\u7684\u4f18\u52bf(Scheme 6d)\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 7a)\u3002\u9996\u5148\uff0cCuII-\u914d\u4f53\u914d\u5408\u7269\u53ef\u80fd\u88ab\u4e09\u7ea7\u80fa\u6216\u82ef\u80fa\u8fd8\u539f\uff0c\u751f\u6210CuI\u914d\u5408\u7269\u3002\u5176\u6b21\uff0cCuI\u914d\u5408\u7269\u4e0e1a\u7684\u53cd\u5e94\u751f\u6210\u4e2d\u95f4\u4f53int-I\u3002\u4e2d\u95f4\u4f53int-I\u7ecf\u5f00\u73af\uff0c\u751f\u6210\u4e24\u6027\u79bb\u5b50int-II\uff0c\u5176\u5171\u632f\u7ed3\u6784\u4e3aint-II’\u3002\u968f\u540e\uff0c\u82ef\u80fa\u4ee5\u5bf9\u6620\u9009\u62e9\u6027\u7684\u65b9\u5f0f\u8fdb\u653bint-II\uff0c\u751f\u6210\u4e2d\u95f4\u4f53int-III\u3002\u6700\u540e\uff0cint-III\u7ecf\u8d28\u5b50\u5316\u540e\uff0c\u4ece\u800c\u83b7\u5f97\u76ee\u6807\u4ea7\u72693a\u3002\u6b64\u5916\uff0c\u4f5c\u8005\u8fd8\u63d0\u51fa\u4e86\u4e24\u79cd\u53ef\u80fd\u7684\u8fc7\u6e21\u6001\uff0c\u7528\u4e8e\u5bf9\u6620\u9009\u62e9\u6027\u8d77\u6e90\u7684\u7814\u7a76(Scheme 7b)\u3002\u5176\u4e2d\uff0cTS-I\u5177\u6709\u7a7a\u95f4\u4f18\u52bf\uff0c\u6709\u5229\u4e8e\u5f62\u6210(S)-3a\u3002\u76f8\u6bd4\u4e4b\u4e0b\uff0cTS-II\u4e0d\u5229\u4e8e\u751f\u6210(R)-3a\uff0c\u53ef\u80fd\u662f\u7531\u4e8e\u914d\u4f53\u4e2d\u7684\u5f02\u4e19\u57fa\u4e0e\u70f7\u6c27\u7fb0\u57fa\u4e4b\u95f4\u7684\u7a7a\u95f4\u4f4d\u963b\u3002 \u603b\u7ed3\uff1a \u4e2d\u56fd\u79d1\u5b66\u9662\u798f\u5efa\u7269\u8d28\u7ed3\u6784\u7814\u7a76\u6240\u7684\u623f\u65b0\u5f3a\u7b49\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u94dc\u50ac\u53161,1,2,2-\u56db\u53d6\u4ee3\u4f9b\u4f53-\u53d7\u4f53\u73af\u4e19\u70f7\u7684\u4e0d\u5bf9\u79f0\u4eb2\u6838\u5f00\u73af\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u624b\u6027\u03b1-\u4e09\u7ea7\u80fa\u884d\u751f\u7269\uff0c\u5177\u6709\u826f\u597d\u81f3\u4f18\u5f02\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0ccopper-acetylide\u4e2d\u95f4\u4f53\u5728\u5b9e\u73b0\u8f6c\u5316\u4e2d\u8d77\u7740\u81f3\u5173\u91cd\u8981\u7684\u4f5c\u7528\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u540e\u671f\u884d\u751f\u5316\u5b9e\u9a8c\u4ee5\u53ca\u76f8\u5173\u751f\u7269\u6d3b\u6027\u5206\u5b50\u7684\u4e0d\u5bf9\u79f0\u5408\u6210\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002\u00a0 \u53c2\u8003\u6587\u732e\uff1a [1] D. Perrotta, M. M. Wang, J. […]","protected":false},"author":26,"featured_media":55386,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"jetpack_post_was_ever_published":false,"_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":false,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_memberships_contains_paid_content":false,"footnotes":"","jetpack_publicize_message":"","jetpack_publicize_feature_enabled":true,"jetpack_social_post_already_shared":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","enabled":false},"version":2}},"categories":[1271],"tags":[4459],"jetpack_publicize_connections":[],"jetpack_featured_media_url":"https:\/\/assets.www.gsbet888.com\/uploads\/2025\/04\/2382c315a6ba396be1932dd8dafaff52.png","jetpack_shortlink":"https:\/\/wp.me\/p96op1-epj","jetpack_sharing_enabled":true,"_links":{"self":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/55385"}],"collection":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/users\/26"}],"replies":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/comments?post=55385"}],"version-history":[{"count":2,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/55385\/revisions"}],"predecessor-version":[{"id":55398,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/55385\/revisions\/55398"}],"wp:featuredmedia":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media\/55386"}],"wp:attachment":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media?parent=55385"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/categories?post=55385"},{"taxonomy":"post_tag","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/tags?post=55385"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}