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\u4f5c\u8005\uff1a\u77f3\u6cb9\u919a<\/strong><\/p>\n

\u3010\u5bfc\u8bfb\u3011<\/strong><\/h4>\n

\u6ce2\u58eb\u987f\u5b66\u9662Hoveyda\/\u5339\u5927\u5218\u9e4f\/\u4e2d\u56fd\u836f\u5927\u5218\u5e86\u8d3a\u56e2\u961f\u5408\u4f5c\u63ed\u793a\u4e86\u4e00\u79cd\u7528\u4e8e\u5408\u6210Z\u5f0fCl,CF3<\/sub>-\u4e09\u53d6\u4ee3\u70ef\u70c3\u7684\u4ea4\u53c9\u590d\u5206\u89e3\u7b56\u7565\uff0c\u4ea7\u7269\u4e2d\u7684C-Cl\u952e\u53ef\u4ee5\u7528\u4e8e\u83b7\u53d6\u66f4\u5927\u8303\u56f4\u7684\u7acb\u4f53\u7279\u5b9a\u7684CF3<\/sub>\u53d6\u4ee3\u70ef\u70c3\u3002\u4ee4\u4eba\u610f\u5916\u7684\u662f\uff0c\u8be5\u53cd\u5e94\u7684\u6548\u7387\u548c\u7acb\u4f53\u9009\u62e9\u6027\u4e0e\u7acb\u4f53\u7ed3\u6784\u4fdd\u6301\u7684\u70ef\u70c3\u590d\u5206\u89e3\u539f\u7406\u76f8\u6096\uff0c\u53ef\u4ee5\u4ee5\u8f83\u597d\u7684\u6536\u7387\u548c\u8f83\u9ad8\u7684\u7acb\u4f53\u9009\u62e9\u6027\u5f97\u5230\u76ee\u6807\u5206\u5b50\u3002\u5177\u4f53\u800c\u8a00\uff0c1\uff09\u94bc\u4e9a\u7532\u57fa\u53ef\u4ee5\u4e0e\u4e09\u53d6\u4ee3\u70ef\u70c3\u5feb\u901f\u53cd\u5e94\uff0c\u4ece\u800c\u907f\u514d\u4e86\u53cc\u5206\u5b50\u5206\u89e3\uff1b2) \u542b\u6709Cl,CF3<\/sub>\u53cc\u53d6\u4ee3\u78b3\u7684\u975e\u5bf9\u6620\u4e09\u53d6\u4ee3mcb\u4e2d\u95f4\u4f53\u4e4b\u95f4\u5b58\u5728\u7684\u80fd\u91cf\u5dee\u5f02\uff0c\u8db3\u4ee5\u5b9e\u73b0\u5b8c\u5168\u7684\u7acb\u4f53\u9009\u62e9\u6027\u3002\u673a\u7406\u7814\u7a76\u7ed9\u51fa\u4e86\u5173\u4e8e\u53cc\u53d6\u4ee3\u70ef\u57fa\u91d1\u5c5e\u7269\u79cd\u7684\u6027\u8d28\u4fe1\u606f\uff0c\u8fd9\u5c06\u4e3a\u6311\u6218\u6027\u7684\u56db\u53d6\u4ee3\u70ef\u70c3\u590d\u5206\u89e3\u53cd\u5e94\u7684\u7814\u7a76\u63d0\u4f9b\u65b0\u7684\u601d\u8def\u548c\u542f\u53d1\u3002<\/p>\n

\n

\u201cSynthesis of Z-gem-Cl,CF3<\/sub>-Substituted Alkenes by Stereoselective Cross-Metathesis and the Role of Disubstituted Mo Alkylidenes<\/p>\n

Qinghe Liu, Can Qin, Jing Wan, Binh Khanh Mai, Xin Zhi Sui, Haruki Kobayashi, Hossein Zahedian, Peng Liu, Amir H. Hoveyda<\/p>\n

J. Am. Chem. Soc.<\/em>,2024<\/strong>, doi:10.1021\/jacs.4c06071\u201d<\/a><\/p>\n<\/blockquote>\n

\<\/p>\n

\u3010\u7814\u7a76\u80cc\u666f\u3011<\/strong><\/h4>\n

\u70ef\u70c3\u7684\u590d\u5206\u89e3\u53cd\u5e94\uff0c\u662f\u6307\u5728\u91d1\u5c5e\u50ac\u5316\u5242\u7684\u4f5c\u7528\u4e0b\uff0c\u4e24\u4e2a\u5e95\u7269\u70ef\u70c3\u4e2d\u7531\u53cc\u952e\u8fde\u63a5\u7684\u4e24\u90e8\u5206\u53d1\u751f\u4ea4\u6362\uff0c\u751f\u6210\u4e86\u4e24\u4e2a\u65b0\u7684\u70ef\u70c3\u7684\u5316\u5b66\u8fc7\u7a0b\u3002\u81ea\u53d1\u73b0\u4ee5\u6765\u4fbf\u5728\u533b\u836f\u548c\u805a\u5408\u7269\u5de5\u4e1a\u4e2d\u6709\u7740\u5e7f\u6cdb\u5e94\u7528\u3002\u76f8\u5bf9\u4e8e\u5176\u4ed6\u53cd\u5e94\uff0c\u8be5\u53cd\u5e94\u526f\u4ea7\u7269\u53ca\u5e9f\u7269\u6392\u653e\u5c11\uff0c\u66f4\u52a0\u73af\u4fdd\u3002<\/p>\n

\u8fd1\u4e9b\u5e74\u6765\uff0c\u542b\u6c1f\u70ef\u70c3\u7684\u590d\u5206\u89e3\u8d8a\u6765\u8d8a\u53d7\u5230\u79d1\u5b66\u5bb6\u4eec\u7684\u5173\u6ce8\uff08Nature<\/em>,2017<\/strong>, 541, 380<\/a>;Nat. Chem.<\/em>2022<\/strong>, 14, 463<\/a>\uff09\u3002\u7a76\u5176\u539f\u56e0\uff0c\u4e3b\u8981\u6709\u4e24\u4e2a\uff1a1\uff09\u542b\u6c1f\u5316\u5408\u7269\u5728\u533b\u836f\u3001\u519c\u836f\u3001\u6750\u6599\u9886\u57df\u4e2d\u7684\u81f3\u5173\u91cd\u8981\u5730\u4f4d\u5df2\u7ecf\u5f97\u5230\u4e86\u8bc1\u660e\uff0c\u4f46\u662f\u81ea\u7136\u754c\u4e2d\u7684\u542b\u6c1f\u5316\u5408\u7269\u6781\u5c11\uff0c\u56e0\u6b64\u6709\u673a\u542b\u6c1f\u5c0f\u5206\u5b50\u4e3b\u8981\u4f9d\u9760\u4eba\u5de5\u5408\u6210\uff1b2\uff09\u70ef\u70c3\u590d\u5206\u89e3\u81ea1967\u5e74\u88abN. Calderon\u7b49\u4eba\u63d0\u51fa\u4ee5\u6765\uff0c\u5728\u542b\u6c1f\u70ef\u70c3\u5c24\u5176\u662f\u4e09\u6c1f\u7532\u57fa\u70ef\u70c3\u7684\u7acb\u4f53\u9009\u62e9\u6027\u5408\u6210\u65b9\u9762\u53ef\u89c1\u7684\u62a5\u9053\u5f88\u5c11\uff0c\u8fd9\u4e3b\u8981\u662f\u4e0e\u50ac\u5316\u5242\u7684\u6d3b\u6027\u3001\u4e09\u6c1f\u7532\u57fa\u8f83\u5927\u7684\u7acb\u4f53\u7535\u5b50\u6548\u5e94\u6709\u5173\u3002\u56e0\u6b64\uff0c\u5982\u4f55\u7a81\u7834\u70ef\u70c3\u590d\u5206\u89e3\u7684\u5408\u6210\u8fb9\u754c\u6210\u4e3a\u4e86\u4e00\u4e2a\u975e\u5e38\u91cd\u8981\u7684\u79d1\u5b66\u547d\u9898\u3002<\/p>\n

\u9274\u4e8e\u6b64\uff0c\u7814\u7a76\u56e2\u961f\u53d1\u5c55\u4e86\u4e00\u79cd\u50ac\u5316\u4ea4\u53c9\u590d\u5206\u89e3\uff08CM\uff09\uff0c\u4ece\u6c14\u4f53\u5c0f\u5206\u5b50\u51fa\u53d1\uff0c\u7528\u4e8e\u5408\u6210\u540c\u65f6\u5177\u6709Cl\u548cCF3<\/sub>\u672b\u7aef\u7684\u4e09\u53d6\u4ee3\u70ef\u70c3\u3002\u8be5\u8fc7\u7a0b\u5177\u6709\u7acb\u4f53\u9009\u62e9\u6027\uff0c\u8fd9\u5b8c\u5168\u4e0d\u540c\u4e8e\u73b0\u6709\u7684\u4e09\u53d6\u4ee3\u70ef\u70c3\u4f5c\u4e3a\u8d77\u59cb\u6750\u6599\u65f6\u7684\u7acb\u4f53\u4fdd\u6301\u7b56\u7565\u3002\u53cd\u5e94\u7531MAP\u50ac\u5316\u5242\u50ac\u5316\uff0c\u5e76\u4e14\u5177\u6709\u5b8c\u5168\u7684Z-\u5f0f\u9009\u62e9\u6027\u3002\u901a\u8fc7\u590d\u5206\u89e3-\u91d1\u5c5e\u5076\u8054\u4e32\u8054\u7b56\u7565\u53ef\u5c06\u4e09\u53d6\u4ee3\u70ef\u70c3\u7684C\u2013Cl\u952e\u8f6c\u5316\u4e3aC\u2013B\u3001C\u2013D\u53ca\u591a\u79cdC\u2013C\u952e\u3002\u7814\u7a76\u4e2d\u53d1\u73b0\u4e86\u4e00\u79cd\u65b0\u7684Cl,CF3<\/sub>-\u4e8c\u53d6\u4ee3\u70ef\u57fa\u94bc\u5316\u5408\u7269\uff0c\u5e76\u4e14\u901a\u8fc7\u5b9e\u9a8c\u548cDFT\u8ba1\u7b97\u7b49\u624b\u6bb5\u9610\u660e\u4e86\u8be5\u7269\u79cd\u7684\u4f5c\u7528\u3002<\/p>\n

\u3010\u7814\u7a76\u4eae\u70b9\u3011<\/h4>\n

\u4e3a\u4e86\u89e3\u51b3\u91d1\u5c5e\u50ac\u5316\u7684\u70ef\u70c3\u590d\u5206\u89e3Cl,CF3<\/sub>-\u4e09\u53d6\u4ee3\u70ef\u70c3\u7684\u7acb\u4f53\u9009\u62e9\u6027\u5408\u6210\u95ee\u9898\uff0c\u7814\u7a76\u8005\u8bbe\u8ba1\u4e86\u56fe1\u6240\u793a\u7684\u50ac\u5316\u5faa\u73af\u7b56\u7565\u3002\u56fe1-left\u63cf\u8ff0\u4e86\u4e8c\u6c2f\u4e09\u6c1f\u4e59\u70ef\u7684stereoretentive\u7b56\u7565\uff0c\u5e76\u4e14\u6307\u51fa\u8f83\u9ad8\u7684\u53cd\u5e94\u80fd\u5792\u662f\u8be5\u7b56\u7565\u6700\u7ec8\u88ab\u653e\u5f03\u7684\u91cd\u8981\u539f\u56e0\u4e4b\u4e00\uff1b\u56fe1-middle\u5c55\u793a\u4e86\u4e00\u6c2f\u4e8c\u6c1f\u4e59\u70efstereoselective\u7b56\u7565\u7684\u4e00\u79cd\u9014\u5f84\uff0c\u5373\u4ece\u5e95\u7269\u5f15\u53d1\uff1b\u56fe1-right\u5c55\u793a\u4e86\u4e00\u6c2f\u4e8c\u6c1f\u4e59\u70efstereoselective\u7b56\u7565\u7684\u53e6\u5916\u4e00\u79cd\u9014\u5f84\uff0c\u5373\u4ece\u4e00\u6c2f\u4e8c\u6c1f\u4e59\u70ef\u5f15\u53d1\u3002<\/p>\n

\<\/p>\n

\u56fe1. \u4e09\u6c1f\u7532\u57fa\u6c2f\u4e59\u70ef\u7684\u50ac\u5316\u5faa\u73af\u7b56\u7565<\/p>\n

\u7814\u7a76\u8005\u901a\u8fc7\u56fe2\u8fdb\u884c\u4e86\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u3002\u4ed6\u4eec\u9009\u62e9\u4e86\u5929\u7136\u4ea7\u7269\u884d\u751f\u7269\u9999\u8305\u9187\u82c4\u57fa\u919a\u548c\u4e09\u6c1f\u7532\u57fa\u6c2f\u4e59\u70ef\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u4ee5\u63a2\u7d22\u8be5stereoselective\u50ac\u5316\u7b56\u7565\u7684\u53ef\u80fd\u6027\u3002\u7ed3\u679c\u8868\u660e\uff0c\u5f53\u4f7f\u7528\u4e09\u79cd\u4e0d\u540c\u7684\u70ef\u57fa\u948c\u4f5c\u4e3a\u50ac\u5316\u5242\u65f6\uff0c\u53ea\u80fd\u89c2\u5bdf\u5230\u5c0f\u4e8e10%\u7684\u76ee\u6807\u4ea7\u7269\u751f\u6210\u3002\u7814\u7a76\u8005\u7ee7\u7eed\u5c1d\u8bd5\u4e86Schrock\u94bc\u50ac\u5316\u5242\u3001\u4ee5\u53cabisaryloxide\u94bc\u50ac\u5316\u5242\uff0c\u5747\u6ca1\u6709\u89c2\u5bdf\u5230\u76ee\u6807\u4ea7\u7269\u7684\u751f\u6210\u3002\u4f46\u662f\uff0c\u5f53\u4f7f\u7528MAC (aryloxide chloride)\u50ac\u5316\u5242\u7684\u65f6\u5019\uff0c\u7814\u7a76\u8005\u89c2\u5bdf\u5230\u4e8625%\u4ea7\u7387\u7684\u4ea4\u53c9\u590d\u5206\u89e3\u4ea7\u7269\u3002\u4f7f\u7528MAP (aryloxide pyrolide)\u50ac\u5316\u5242\u4ee3\u66ffMAC\u50ac\u5316\u5242\u540e\uff0c\u4ea4\u53c9\u590d\u5206\u89e3\u4ea7\u7269\u7684\u4ea7\u7387\u5f97\u5230\u4e86\u8fdb\u4e00\u6b65\u7684\u63d0\u5347\u3002\u603b\u4f53\u6765\u8bf4\uff0c\u56fe2\u63ed\u793a\u4e86\u50ac\u5316\u5242\u7684\u79cd\u7c7b\u5728\u5b9e\u73b0\u542b\u6c1f\u70ef\u70c3\u590d\u5206\u89e3\u53cd\u5e94\u7684\u65f6\u5019\u81f3\u5173\u91cd\u8981\uff0c\u5e76\u4e14\u5b9e\u73b0\u4e86\u8f83\u9ad8\u7684\u7acb\u4f53\u9009\u62e9\u6027\u63a7\u5236\u3002<\/p>\n

\<\/p>\n

\u56fe2. \u591a\u79cd\u50ac\u5316\u4f53\u7cfb\u7684\u5c1d\u8bd5<\/p>\n

\u8fd9\u9879\u7814\u7a76\u65e8\u5728\u5efa\u7acb\u4e09\u53d6\u4ee3\u4e09\u6c1f\u70ef\u70c3\u7684\u9ad8\u6548\u9ad8\u7acb\u4f53\u9009\u62e9\u6027\u5408\u6210\u7b56\u7565\u3002\u5728\u56fe3\u4e2d\uff0c\u7814\u7a76\u8005\u5c55\u793a\u4e86\u53cd\u5e94\u4ea7\u7269\u7684\u5408\u6210\u5e94\u7528\u3002\u4ed6\u4eec\u9996\u5148\u5c06\u4ea4\u53c9\u590d\u5206\u89e3\u4e0eSuzuki coupling\u4e32\u8054\uff0c\u5b9e\u73b0\u4e86C-Cl\u952e\u5411C-B\u7684\u8f6c\u5316\uff1b\u4e0eNegishi coupling\u4e32\u8054\uff0c\u5b9e\u73b0\u4e86C-Cl\u952e\u5411C-C\u952e\u7684\u8f6c\u5316\uff1b\u4e0eStille coupling\u4e32\u8054\uff0c\u5b9e\u73b0\u4e86alllylation\u548ccarbonylation\uff1b\u4e0e\u5fae\u6ce2\u53cd\u5e94\u7ed3\u5408\uff0c\u5b9e\u73b0\u4e86C-Cl\u952e\u5411C-D\u7684\u9ad8\u6548\u8f6c\u5316\u3002<\/p>\n

\<\/p>\n

\u56fe3. CC\u4e0eCM\u7684\u4e32\u8054\u7b56\u7565<\/p>\n

\u63a5\u4e0b\u6765\uff0c\u7814\u7a76\u4eba\u5458\u5bf9\u53cd\u5e94\u4e2d\u9996\u6b21\u89c2\u5bdf\u5230\u7684Cl,CF3<\/sub>-\u4e8c\u53d6\u4ee3\u70ef\u57fa\u94bc\u7269\u79cd\u8fdb\u884c\u4e86\u6df1\u5165\u7684\u7814\u7a76\u3002\u9996\u5148\uff0cMAP\u50ac\u5316\u5242\u4e0e50\u5f53\u91cf\u7684\u4e09\u6c1f\u7532\u57fa\u4e59\u70ef\u53cd\u5e94\uff0c\u539f\u4f4d\u4ea7\u751f\u7684Cl,CF3<\/sub>-\u4e8c\u53d6\u4ee3\u70ef\u57fa\u94bc\u7269\u79cd\u88ab\u52a0\u5165\u7684bipyridine\u6355\u83b7\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u5c06MAP\u50ac\u5316\u5242\u4e0e\u5421\u5576\u76d0\u53cd\u5e94\uff0c\u751f\u6210\u76f8\u5e94\u7684MAC\u91d1\u5c5e\u7edc\u5408\u7269\uff0c\u6700\u540e\u52a0\u5165\u4e09\u6c1f\u7532\u57fa\u4e59\u70ef\uff0c\u4ee535%\u7684\u6536\u7387\u5206\u79bb\u5f97\u5230\u6c2f\u79bb\u5b50\u914d\u4f4d\u7684Cl,CF3<\/sub>-\u4e8c\u53d6\u4ee3\u70ef\u57fa\u94bc\u7269\u79cd\u3002\u4ed6\u4eec\u901a\u8fc7\u6838\u78c1\u548c\u5143\u7d20\u5206\u6790\u7b49\u624b\u6bb5\u5bf9\u6355\u83b7\u7684\u7a33\u5b9a\u7269\u79cd\u8fdb\u884c\u4e86\u9a8c\u8bc1\uff0c\u8bc1\u5b9e\u4e86\u8be5\u7c7bCl,CF3<\/sub>-\u4e8c\u53d6\u4ee3\u70ef\u57fa\u94bc\u7269\u79cd\u3002<\/p>\n

\<\/p>\n

\u56fe4. Cl,CF3<\/sub>-\u4e8c\u53d6\u4ee3\u70ef\u57fa\u94bc\u7269\u79cd\u7684\u53d1\u73b0\u4e0e\u786e\u8bc1<\/p>\n

\u3010\u7814\u7a76\u7ed3\u8bba\u3011<\/h4>\n

\u672c\u6587\u63ed\u793a\u4e86\u4e00\u79cd\u7528\u4e8e\u5408\u6210Z\u5f0fCl,CF3<\/sub>-\u4e09\u53d6\u4ee3\u70ef\u70c3\u7684\u4ea4\u53c9\u590d\u5206\u89e3\u7b56\u7565\uff0c\u4ea7\u7269\u4e2d\u7684C-Cl\u952e\u53ef\u4ee5\u7528\u4e8e\u83b7\u53d6\u66f4\u5927\u8303\u56f4\u7684\u7acb\u4f53\u7279\u5b9a\u7684CF3<\/sub>\u53d6\u4ee3\u70ef\u70c3\u3002\u4ee4\u4eba\u610f\u5916\u7684\u662f\uff0c\u8be5\u53cd\u5e94\u7684\u6548\u7387\u548c\u7acb\u4f53\u9009\u62e9\u6027\u4e0e\u7acb\u4f53\u7ed3\u6784\u4fdd\u6301\u7684\u70ef\u70c3\u590d\u5206\u89e3\u539f\u7406\u76f8\u6096\uff0c\u53ef\u4ee5\u4ee5\u8f83\u597d\u7684\u6536\u7387\u548c\u8f83\u9ad8\u7684\u7acb\u4f53\u9009\u62e9\u6027\u5f97\u5230\u76ee\u6807\u5206\u5b50\u3002\u5177\u4f53\u800c\u8a00\uff0c1\uff09\u94bc\u4e9a\u7532\u57fa\u53ef\u4ee5\u4e0e\u4e09\u53d6\u4ee3\u70ef\u70c3\u5feb\u901f\u53cd\u5e94\uff0c\u4ece\u800c\u907f\u514d\u4e86\u53cc\u5206\u5b50\u5206\u89e3\uff1b2) \u542b\u6709Cl,CF3<\/sub>\u53cc\u53d6\u4ee3\u78b3\u7684\u975e\u5bf9\u6620\u4e09\u53d6\u4ee3mcb\u4e2d\u95f4\u4f53\u4e4b\u95f4\u5b58\u5728\u7684\u80fd\u91cf\u5dee\u5f02\uff0c\u8db3\u4ee5\u5b9e\u73b0\u5b8c\u5168\u7684\u7acb\u4f53\u9009\u62e9\u6027\u3002\u673a\u7406\u7814\u7a76\u7ed9\u51fa\u4e86\u5173\u4e8e\u53cc\u53d6\u4ee3\u70ef\u57fa\u91d1\u5c5e\u7269\u79cd\u7684\u6027\u8d28\u4fe1\u606f\uff0c\u8fd9\u5c06\u4e3a\u6311\u6218\u6027\u7684\u56db\u53d6\u4ee3\u70ef\u70c3\u590d\u5206\u89e3\u53cd\u5e94\u7684\u7814\u7a76\u63d0\u4f9b\u65b0\u7684\u601d\u8def\u548c\u542f\u53d1\u3002<\/p>\n

(\u975e\u5e38\u611f\u8c22\u5218\u5e86\u8d3a\u6559\u6388\u5bf9<\/strong>Chem-Station<\/strong>\u7684\u652f\u6301<\/strong>)<\/p>\n","protected":false},"excerpt":{"rendered":"\u4f5c\u8005\uff1a\u77f3\u6cb9\u919a \u3010\u5bfc\u8bfb\u3011 \u6ce2\u58eb\u987f\u5b66\u9662Hoveyda\/\u5339\u5927\u5218\u9e4f\/\u4e2d\u56fd\u836f\u5927\u5218\u5e86\u8d3a\u56e2\u961f\u5408\u4f5c\u63ed\u793a\u4e86\u4e00\u79cd\u7528\u4e8e\u5408\u6210Z\u5f0fCl,CF3-\u4e09\u53d6\u4ee3\u70ef\u70c3\u7684\u4ea4\u53c9\u590d\u5206\u89e3\u7b56\u7565\uff0c\u4ea7\u7269\u4e2d\u7684C-Cl\u952e\u53ef\u4ee5\u7528\u4e8e\u83b7\u53d6\u66f4\u5927\u8303\u56f4\u7684\u7acb\u4f53\u7279\u5b9a\u7684CF3\u53d6\u4ee3\u70ef\u70c3\u3002\u4ee4\u4eba\u610f\u5916\u7684\u662f\uff0c\u8be5\u53cd\u5e94\u7684\u6548\u7387\u548c\u7acb\u4f53\u9009\u62e9\u6027\u4e0e\u7acb\u4f53\u7ed3\u6784\u4fdd\u6301\u7684\u70ef\u70c3\u590d\u5206\u89e3\u539f\u7406\u76f8\u6096\uff0c\u53ef\u4ee5\u4ee5\u8f83\u597d\u7684\u6536\u7387\u548c\u8f83\u9ad8\u7684\u7acb\u4f53\u9009\u62e9\u6027\u5f97\u5230\u76ee\u6807\u5206\u5b50\u3002\u5177\u4f53\u800c\u8a00\uff0c1\uff09\u94bc\u4e9a\u7532\u57fa\u53ef\u4ee5\u4e0e\u4e09\u53d6\u4ee3\u70ef\u70c3\u5feb\u901f\u53cd\u5e94\uff0c\u4ece\u800c\u907f\u514d\u4e86\u53cc\u5206\u5b50\u5206\u89e3\uff1b2) \u542b\u6709Cl,CF3\u53cc\u53d6\u4ee3\u78b3\u7684\u975e\u5bf9\u6620\u4e09\u53d6\u4ee3mcb\u4e2d\u95f4\u4f53\u4e4b\u95f4\u5b58\u5728\u7684\u80fd\u91cf\u5dee\u5f02\uff0c\u8db3\u4ee5\u5b9e\u73b0\u5b8c\u5168\u7684\u7acb\u4f53\u9009\u62e9\u6027\u3002\u673a\u7406\u7814\u7a76\u7ed9\u51fa\u4e86\u5173\u4e8e\u53cc\u53d6\u4ee3\u70ef\u57fa\u91d1\u5c5e\u7269\u79cd\u7684\u6027\u8d28\u4fe1\u606f\uff0c\u8fd9\u5c06\u4e3a\u6311\u6218\u6027\u7684\u56db\u53d6\u4ee3\u70ef\u70c3\u590d\u5206\u89e3\u53cd\u5e94\u7684\u7814\u7a76\u63d0\u4f9b\u65b0\u7684\u601d\u8def\u548c\u542f\u53d1\u3002 \u201cSynthesis of Z-gem-Cl,CF3-Substituted Alkenes by Stereoselective Cross-Metathesis and the Role of Disubstituted Mo Alkylidenes Qinghe Liu, Can Qin, Jing Wan, Binh Khanh Mai, Xin Zhi Sui, Haruki Kobayashi, Hossein Zahedian, Peng Liu, Amir H. Hoveyda J. Am. Chem. Soc., 2024, doi:10.1021\/jacs.4c06071\u201d \u3010\u7814\u7a76\u80cc\u666f\u3011 \u70ef\u70c3\u7684\u590d\u5206\u89e3\u53cd\u5e94\uff0c\u662f\u6307\u5728\u91d1\u5c5e\u50ac\u5316\u5242\u7684\u4f5c\u7528\u4e0b\uff0c\u4e24\u4e2a\u5e95\u7269\u70ef\u70c3\u4e2d\u7531\u53cc\u952e\u8fde\u63a5\u7684\u4e24\u90e8\u5206\u53d1\u751f\u4ea4\u6362\uff0c\u751f\u6210\u4e86\u4e24\u4e2a\u65b0\u7684\u70ef\u70c3\u7684\u5316\u5b66\u8fc7\u7a0b\u3002\u81ea\u53d1\u73b0\u4ee5\u6765\u4fbf\u5728\u533b\u836f\u548c\u805a\u5408\u7269\u5de5\u4e1a\u4e2d\u6709\u7740\u5e7f\u6cdb\u5e94\u7528\u3002\u76f8\u5bf9\u4e8e\u5176\u4ed6\u53cd\u5e94\uff0c\u8be5\u53cd\u5e94\u526f\u4ea7\u7269\u53ca\u5e9f\u7269\u6392\u653e\u5c11\uff0c\u66f4\u52a0\u73af\u4fdd\u3002 \u8fd1\u4e9b\u5e74\u6765\uff0c\u542b\u6c1f\u70ef\u70c3\u7684\u590d\u5206\u89e3\u8d8a\u6765\u8d8a\u53d7\u5230\u79d1\u5b66\u5bb6\u4eec\u7684\u5173\u6ce8\uff08Nature, 2017, 541, 380; Nat. Chem. 2022, 14, 463\uff09\u3002\u7a76\u5176\u539f\u56e0\uff0c\u4e3b\u8981\u6709\u4e24\u4e2a\uff1a1\uff09\u542b\u6c1f\u5316\u5408\u7269\u5728\u533b\u836f\u3001\u519c\u836f\u3001\u6750\u6599\u9886\u57df\u4e2d\u7684\u81f3\u5173\u91cd\u8981\u5730\u4f4d\u5df2\u7ecf\u5f97\u5230\u4e86\u8bc1\u660e\uff0c\u4f46\u662f\u81ea\u7136\u754c\u4e2d\u7684\u542b\u6c1f\u5316\u5408\u7269\u6781\u5c11\uff0c\u56e0\u6b64\u6709\u673a\u542b\u6c1f\u5c0f\u5206\u5b50\u4e3b\u8981\u4f9d\u9760\u4eba\u5de5\u5408\u6210\uff1b2\uff09\u70ef\u70c3\u590d\u5206\u89e3\u81ea1967\u5e74\u88abN. Calderon\u7b49\u4eba\u63d0\u51fa\u4ee5\u6765\uff0c\u5728\u542b\u6c1f\u70ef\u70c3\u5c24\u5176\u662f\u4e09\u6c1f\u7532\u57fa\u70ef\u70c3\u7684\u7acb\u4f53\u9009\u62e9\u6027\u5408\u6210\u65b9\u9762\u53ef\u89c1\u7684\u62a5\u9053\u5f88\u5c11\uff0c\u8fd9\u4e3b\u8981\u662f\u4e0e\u50ac\u5316\u5242\u7684\u6d3b\u6027\u3001\u4e09\u6c1f\u7532\u57fa\u8f83\u5927\u7684\u7acb\u4f53\u7535\u5b50\u6548\u5e94\u6709\u5173\u3002\u56e0\u6b64\uff0c\u5982\u4f55\u7a81\u7834\u70ef\u70c3\u590d\u5206\u89e3\u7684\u5408\u6210\u8fb9\u754c\u6210\u4e3a\u4e86\u4e00\u4e2a\u975e\u5e38\u91cd\u8981\u7684\u79d1\u5b66\u547d\u9898\u3002 \u9274\u4e8e\u6b64\uff0c\u7814\u7a76\u56e2\u961f\u53d1\u5c55\u4e86\u4e00\u79cd\u50ac\u5316\u4ea4\u53c9\u590d\u5206\u89e3\uff08CM\uff09\uff0c\u4ece\u6c14\u4f53\u5c0f\u5206\u5b50\u51fa\u53d1\uff0c\u7528\u4e8e\u5408\u6210\u540c\u65f6\u5177\u6709Cl\u548cCF3\u672b\u7aef\u7684\u4e09\u53d6\u4ee3\u70ef\u70c3\u3002\u8be5\u8fc7\u7a0b\u5177\u6709\u7acb\u4f53\u9009\u62e9\u6027\uff0c\u8fd9\u5b8c\u5168\u4e0d\u540c\u4e8e\u73b0\u6709\u7684\u4e09\u53d6\u4ee3\u70ef\u70c3\u4f5c\u4e3a\u8d77\u59cb\u6750\u6599\u65f6\u7684\u7acb\u4f53\u4fdd\u6301\u7b56\u7565\u3002\u53cd\u5e94\u7531MAP\u50ac\u5316\u5242\u50ac\u5316\uff0c\u5e76\u4e14\u5177\u6709\u5b8c\u5168\u7684Z-\u5f0f\u9009\u62e9\u6027\u3002\u901a\u8fc7\u590d\u5206\u89e3-\u91d1\u5c5e\u5076\u8054\u4e32\u8054\u7b56\u7565\u53ef\u5c06\u4e09\u53d6\u4ee3\u70ef\u70c3\u7684C\u2013Cl\u952e\u8f6c\u5316\u4e3aC\u2013B\u3001C\u2013D\u53ca\u591a\u79cdC\u2013C\u952e\u3002\u7814\u7a76\u4e2d\u53d1\u73b0\u4e86\u4e00\u79cd\u65b0\u7684Cl,CF3-\u4e8c\u53d6\u4ee3\u70ef\u57fa\u94bc\u5316\u5408\u7269\uff0c\u5e76\u4e14\u901a\u8fc7\u5b9e\u9a8c\u548cDFT\u8ba1\u7b97\u7b49\u624b\u6bb5\u9610\u660e\u4e86\u8be5\u7269\u79cd\u7684\u4f5c\u7528\u3002 \u3010\u7814\u7a76\u4eae\u70b9\u3011 \u4e3a\u4e86\u89e3\u51b3\u91d1\u5c5e\u50ac\u5316\u7684\u70ef\u70c3\u590d\u5206\u89e3Cl,CF3-\u4e09\u53d6\u4ee3\u70ef\u70c3\u7684\u7acb\u4f53\u9009\u62e9\u6027\u5408\u6210\u95ee\u9898\uff0c\u7814\u7a76\u8005\u8bbe\u8ba1\u4e86\u56fe1\u6240\u793a\u7684\u50ac\u5316\u5faa\u73af\u7b56\u7565\u3002\u56fe1-left\u63cf\u8ff0\u4e86\u4e8c\u6c2f\u4e09\u6c1f\u4e59\u70ef\u7684stereoretentive\u7b56\u7565\uff0c\u5e76\u4e14\u6307\u51fa\u8f83\u9ad8\u7684\u53cd\u5e94\u80fd\u5792\u662f\u8be5\u7b56\u7565\u6700\u7ec8\u88ab\u653e\u5f03\u7684\u91cd\u8981\u539f\u56e0\u4e4b\u4e00\uff1b\u56fe1-middle\u5c55\u793a\u4e86\u4e00\u6c2f\u4e8c\u6c1f\u4e59\u70efstereoselective\u7b56\u7565\u7684\u4e00\u79cd\u9014\u5f84\uff0c\u5373\u4ece\u5e95\u7269\u5f15\u53d1\uff1b\u56fe1-right\u5c55\u793a\u4e86\u4e00\u6c2f\u4e8c\u6c1f\u4e59\u70efstereoselective\u7b56\u7565\u7684\u53e6\u5916\u4e00\u79cd\u9014\u5f84\uff0c\u5373\u4ece\u4e00\u6c2f\u4e8c\u6c1f\u4e59\u70ef\u5f15\u53d1\u3002 \u56fe1. \u4e09\u6c1f\u7532\u57fa\u6c2f\u4e59\u70ef\u7684\u50ac\u5316\u5faa\u73af\u7b56\u7565 \u7814\u7a76\u8005\u901a\u8fc7\u56fe2\u8fdb\u884c\u4e86\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u3002\u4ed6\u4eec\u9009\u62e9\u4e86\u5929\u7136\u4ea7\u7269\u884d\u751f\u7269\u9999\u8305\u9187\u82c4\u57fa\u919a\u548c\u4e09\u6c1f\u7532\u57fa\u6c2f\u4e59\u70ef\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u4ee5\u63a2\u7d22\u8be5stereoselective\u50ac\u5316\u7b56\u7565\u7684\u53ef\u80fd\u6027\u3002\u7ed3\u679c\u8868\u660e\uff0c\u5f53\u4f7f\u7528\u4e09\u79cd\u4e0d\u540c\u7684\u70ef\u57fa\u948c\u4f5c\u4e3a\u50ac\u5316\u5242\u65f6\uff0c\u53ea\u80fd\u89c2\u5bdf\u5230\u5c0f\u4e8e10%\u7684\u76ee\u6807\u4ea7\u7269\u751f\u6210\u3002\u7814\u7a76\u8005\u7ee7\u7eed\u5c1d\u8bd5\u4e86Schrock\u94bc\u50ac\u5316\u5242\u3001\u4ee5\u53cabisaryloxide\u94bc\u50ac\u5316\u5242\uff0c\u5747\u6ca1\u6709\u89c2\u5bdf\u5230\u76ee\u6807\u4ea7\u7269\u7684\u751f\u6210\u3002\u4f46\u662f\uff0c\u5f53\u4f7f\u7528MAC (aryloxide 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