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\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749<\/p>\n

\u5bfc\u8bfb<\/h4>\n

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Visible-Light-Driven Reductive Carboarylation of Styrenes with CO2<\/sub> and Aryl Halides<\/p>\n

Hao Wang, Yuzhen Gao, Chunlin Zhou, and Gang Li<\/p>\n

J. Am. Chem. Soc.<\/em> ASAP DOI: 10.1021\/jacs.0c03144<\/a><\/p><\/blockquote>\n

\"\"<\/a><\/p>\n

\u6b63\u6587<\/h4>\n

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\u8fd1\u5e74\u6765\uff0cCO2<\/sub>\u4f5c\u4e3a\u4e00\u79cd\u53ef\u6301\u7eed\u3001\u4e30\u5bcc\u3001\u4f4e\u6210\u672c\u3001\u65e0\u6bd2\u7684\u539f\u6599\uff0c\u4e00\u76f4\u4f5c\u4e3a\u5316\u5b66\u5408\u6210\u9886\u57df\u7684\u7814\u7a76\u70ed\u70b9\uff0c\u800c\u5229\u7528\u5149\u50ac\u5316\uff0c\u53ef\u4ee5\u5f88\u597d\u5c06\u5176\u5f15\u5165\u53cd\u5e94\u4f53\u7cfb\u4e2d\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u4ec5\u6709\u5c11\u91cf\u6587\u732e\u5df2\u62a5\u9053\u5173\u4e8e\u4f7f\u7528\u4e2d\u6027\u5149\u50ac\u5316\u5242\uff0c\u5b9e\u73b0CO2<\/sub>\u4e0e\u70ef\u70c3\u7684\u53cc\u5b98\u80fd\u5316\u53cd\u5e94\uff0c\u83b7\u5f97\u4e00\u4e9b\u5177\u6709\u4ef7\u503c\u7684\u7fa7\u9178\u884d\u751f\u7269\uff08Scheme 1b\uff09\u3002\u6b64\u5916\uff0c\u5176\u4ed6\u8bfe\u9898\u7ec4\u4e5f\u62a5\u9053\u4e86\u4f7f\u7528CO2<\/sub>\u4e0e\u5404\u79cd\u81ea\u7531\u57fa\u524d\u4f53\u53cd\u5e94\uff0c\u7ecf\u53ef\u89c1\u5149\u8bf1\u5bfc\uff0c\u5b9e\u73b0\u533a\u57df\u9009\u62e9\u6027\u7684\u78b3\u7fa7\u5316\u3001\u7845\u70f7\u57fa\u5316\u3001\u81a6\u9170\u57fa\u7fa7\u5316\u3001\u70ef\u70c3\u7684\u786b\u4ee3\u7fa7\u5316\u7b49\u8fc7\u7a0b\u3002\u7136\u800c\uff0c\u8fd9\u4e9b\u5149\u50ac\u5316\u4f53\u7cfb\u5747\u4e0d\u9002\u7528\u4e8eCO2<\/sub>\u3001\u82b3\u57fa\u5364\u5316\u7269\u3001\u70ef\u70c3\u7684\u4e09\u7ec4\u5206\u82b3\u57fa\u5316\u53cd\u5e94\uff0c\u56e0\u4e3a\u8981\u4f7f\u82b3\u57fa\u5364\u5316\u7269\u53c2\u4e0e\u6b64\u7c7b\u53cd\u5e94\uff0c\u5fc5\u987b\u4f7f\u7528\u4e00\u79cd\u65b0\u9896\u7684\u9ad8\u5ea6\u8fd8\u539f\u7684\u50ac\u5316\u5242\u3002\u57fa\u4e8e\u8fd9\u4e00\u6311\u6218\uff0c\u5c1a\u672a\u6709\u6587\u732e\u62a5\u9053\u5173\u4e8e\u901a\u8fc7\u53ef\u89c1\u5149\u4fc3\u8fdb\u70ef\u70c3\u3001CO2<\/sub>\u548c\u82b3\u57fa\u5364\u5316\u7269\u7684Meerwein\u82b3\u57fa\u5316\u7fb0\u57fa\u5316\u53cd\u5e94\u3002\u5728\u6b64\uff0c\u4e2d\u79d1\u9662\uff08\u798f\u5efa\u7269\u8d28\u7ed3\u6784\u7814\u7a76\u6240\uff09\u674e\u7eb2\u6559\u6388\u8bfe\u9898\u7ec4\u9996\u6b21\u63d0\u51fa\u4f7f\u7528\u53ef\u89c1\u5149\u4f5c\u4e3a\u50ac\u5316\u5242\uff0c\u4f7f\u7528\u5ec9\u4ef7\u7684HCO2<\/sub>K\u4f5c\u4e3a\u672b\u7aef\u8fd8\u539f\u5242\uff0c\u53ef\u5b9e\u73b0\u82ef\u4e59\u70ef\u3001CO2<\/sub>\u3001\u82b3\u57fa\u5364\u5316\u7269\u7684\u9ad8\u5ea6\u533a\u57df\u9009\u62e9\u6027\u7684\u8fd8\u7fb0\u57fa\u5316\u53cd\u5e94\uff0c\u83b7\u5f97\u591a\u79cd\u5177\u6709\u4ef7\u503c\u7684\u6c22\u5316\u8089\u6842\u9178\u884d\u751f\u7269 \u3002\u6b64\u5916\uff0c\u8be5\u82b3\u57fa\u5364\u5316\u7269\u7684\u8303\u56f4\u53ef\u8fdb\u4e00\u6b65\u6269\u5c55\u5230\u5421\u5576\u57fa\u5364\u5316\u7269\u3001\u70f7\u57fa\u5364\u5316\u7269\u751a\u81f3\u82b3\u57fa\u6c2f\u5316\u7269\u7b49\uff08Scheme 1c\uff09\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u9996\u5148\uff0c\u4f5c\u8005\u4ee51,1-\u4e8c\u82ef\u57fa\u4e59\u70ef\u3001<\/strong>\u7898\u82ef\u548cCO2<\/sub>\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u4e86\u76f8\u5173\u7fb0\u57fa\u5316\u53cd\u5e94\u6761\u4ef6\u7684\u7b5b\u9009\uff08Table 1\uff09\u3002\u00a0\u7ecf\u5927\u91cf\u53cd\u5e94\u6761\u4ef6\u7b5b\u9009\u4e4b\u540e\uff0c\u5f53\u4ee5DABCO\u4f5c\u4e3a\u6c22\u539f\u5b50\u8f6c\u79fb\u50ac\u5316\u5242\uff0c[Ir(ppy)2<\/sub>(dtbbpy)]PF6<\/sub>\u4f5c\u4e3a\u5149\u50ac\u5316\u5242\uff0cHCO2<\/sub>K\u4f5c\u4e3a\u672b\u7aef\u8fd8\u539f\u5242\uff0cK2<\/sub>CO3<\/sub>\u4f5c\u4e3a\u78b1\uff0c\u53ef\u5728DMSO\u6eb6\u5242\u4e2d\uff0c\u83b7\u5f9778\uff05\u6536\u7387\u7684\u76ee\u6807\u4ea7\u72691<\/strong>\uff08entry 1\uff09\u3002\u6b64\u5916\uff0c\u4e3a\u4e86\u4fbf\u4e8e\u5206\u6790\u548c\u5206\u79bb\u4ea7\u7269\uff0c\u4f5c\u8005\u5c06\u539f\u59cb\u7684\u7fa7\u9178\u4ea7\u7269\u8f6c\u5316\u4e3a\u7532\u916f\u3002\u5f53\u4e0d\u4f7f\u7528\u5149\u50ac\u5316\u5242\u6216\u5728\u65e0\u5149\u7684\u6761\u4ef6\u4e0b\uff0c\u5747\u672a\u68c0\u6d4b\u5230\u4ea7\u7269\uff0c\u4ece\u800c\u8868\u660e\u53cd\u5e94\u9700\u7531\u5149\u8bf1\u5bfc\uff08entries 2-3\uff09\u3002\u800c\u5728\u6c2e\u6c14\u6c14\u4f53\u4e2d\u53cd\u5e94\u65f6\uff0c\u6536\u7387\u7565\u6709\u4e0b\u964d\uff0c\u8868\u660eHCO2<\/sub>K\u7684\u6c27\u5316\u6216K2<\/sub>CO3<\/sub>\u7684\u9178\u5316\u4e5f\u53ef\u80fd\u5f62\u6210CO2<\/sub>\uff08entry 4\uff09\u3002\u5728\u4e0d\u5b58\u5728\u672b\u7aef\u8fd8\u539f\u5242HCO2<\/sub>K\u65f6\uff0c\u5219\u65e0\u6cd5\u83b7\u5f97\u4efb\u4f55\u4ea7\u7269\uff08entry 5\uff09\u3002\u5f53\u4f7f\u75282.5\u5f53\u91cf\u7684DABCO\uff0c\u4f46\u4f53\u7cfb\u4e2d\u4e0d\u5b58\u5728HCO2<\/sub>K\uff0c\u53ea\u80fd\u5f62\u6210\u75d5\u91cf\u7684\u4ea7\u7269\uff08entry 6\uff09\u3002\u800c\u5bf9\u5176\u5b83HAT\u50ac\u5316\u5242\u7b5b\u9009\u540e\uff0cDABCO\u5177\u6709\u8f83\u9ad8\u7684\u50ac\u5316\u6d3b\u6027\uff08entries 7-10\uff09\u3002\u8fd9\u4e9b\u7ed3\u679c\u53ef\u80fd\u8868\u660e\uff0cHCO2<\/sub>K\/DABCO\u7684\u7ed3\u5408\u4f5c\u4e3a\u8be5\u8fd8\u539f\u7fb0\u57fa\u5316\u53cd\u5e94\u4e2d\u6709\u6548\u7684\u7535\u5b50\u4f9b\u4f53\u3002\u6b64\u5916\uff0cK2<\/sub>CO3<\/sub>\u5bf9\u4e8e\u8be5\u53cd\u5e94\u4ec5\u7a0d\u6709\u76ca\u5904\uff08entry 11\uff09\uff0c\u800c\u5176\u4ed6\u78b1\uff08\u5982Na2<\/sub>CO3<\/sub>\u548cCs2<\/sub>CO3<\/sub>\uff09\u4e5f\u540c\u6837\u6709\u6548\uff08entries 12-13\uff09\u3002\u6700\u540e\uff0c\u4f5c\u8005\u4e5f\u5bf9\u6eb6\u5242\u8fdb\u884c\u7b5b\u9009\uff08DMF\u3001DMA\uff09\uff0c\u53d1\u73b0DMSO\u4f5c\u4e3a\u6700\u4f73\u6eb6\u5242\uff08entries 14-15\uff09\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u5728\u83b7\u5f97\u4e0a\u8ff0\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u540e\uff0c\u4f5c\u8005\u56fa\u5b9a1,1-\u4e8c\u82ef\u4e59\u70ef\uff0c\u5f00\u59cb\u5bf9\u5404\u79cd\u82b3\u57fa\u7898\u5316\u7269\u548c\u6eb4\u5316\u7269\u4ee5\u53ca\u4e00\u4e9b\u5177\u6709\u4ee3\u8868\u6027\u7684\u70f7\u57fa\u5364\u5316\u7269\u8fdb\u884c\u4e86\u6269\u5c55\uff08Table 2\uff09\u3002\u9996\u5148\uff0c\u4f7f\u7528\u5ec9\u4ef7\u7684\u6eb4\u82ef\u4ec5\u6bd4\u7898\u82ef\u83b7\u5f97\u4ea7\u72691<\/strong>\u7684\u6536\u7387\u7a0d\u5dee\u4e9b\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5728\u8be5\u53cd\u5e94\u4f53\u7cfb\u4e2d\u4e0d\u53d7\u7535\u5b50\u6548\u5e94\u7684\u5f71\u54cd\uff0c\u5747\u53ef\u83b7\u5f97\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u72692<\/strong>–33<\/strong>\uff0c\u5982\u7ed9\u7535\u5b50\u57fa\uff08\u7532\u57fa\u3001\u7532\u6c27\u57fa\u3001\u7532\u786b\u57fa\u7b49\uff09\uff0c\u5438\u7535\u5b50\u57fa\uff08\u6c1f\u3001\u6c2f\u4ee3\u3001\u787c\u9178\u916f\u3001\u4e09\u6c1f\u7532\u57fa\u3001\u7fb0\u57fa\u3001\u6c30\u57fa\u7b49\uff09\u3002\u4f46\u662f\uff0c\u4e00\u4e9b\u5e26\u6709\u7ed9\u7535\u5b50\u57fa\u56e2\u7684\u5e95\u7269\uff08\u5982\u4ea7\u72692<\/strong>–5<\/strong>\u7684\u5364\u5316\u7269\uff09\uff0c\u82b3\u57fa\u7898\u5316\u7269\u7684\u6536\u7387\u9ad8\u4e8e\u82b3\u57fa\u6eb4\u5316\u7269\u3002\u540c\u6837\uff0c\u5bf9\u4e8e\u67d0\u4e9b\u5177\u6709\u5438\u7535\u5b50\u57fa\u56e2\u7684\u5e95\u7269\uff0c\u5982\u4ea7\u726925<\/strong>\u300128<\/strong>\u548c32<\/strong>\u7684\u6eb4\u5316\u7269\uff0c\u82b3\u57fa\u6eb4\u5316\u7269\u7684\u6536\u7387\u9ad8\u4e8e\u82b3\u57fa\u7898\u5316\u7269\u3002\u800c\u4e14\uff0c\u90bb\u4f4d\u53d6\u4ee3\u7684\u82b3\u57fa\u5364\u5316\u7269\u901a\u5e38\u6bd4\u95f4\u4f4d\u548c\u5bf9\u4f4d\u53d6\u4ee3\u7684\u7684\u4ea7\u7269\u6536\u7387\u504f\u4f4e\uff0c\u5982\u4ea7\u72695<\/strong>–7<\/strong>\u300112<\/strong>–14<\/strong>\u548c28<\/strong>–30<\/strong>\u3002\u6b64\u5916\uff0c\u7898\u4ee3\u8418\uff0834<\/strong>\uff09\u548c\u6eb4\u4ee3\u8418\uff0835<\/strong>\uff09\u4e5f\u4e0e\u4f53\u7cfb\u517c\u5bb9\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5e26\u6709\u6c2f\u6216\u787c\u9178\u916f\u57fa\u56e2\u7684\u82b3\u57fa\u7898\u5316\u7269\/\u6eb4\u5316\u7269\u5e95\u7269\u4e5f\u53ef\u4e0e\u4f53\u7cfb\u517c\u5bb9\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u726915<\/strong>–18<\/strong>\uff0c\u4e3a\u8fdb\u4e00\u6b65\u884d\u751f\u5316\u63d0\u4f9b\u4e86\u591a\u79cd\u53ef\u80fd\u3002\u968f\u540e\uff0c\u4f5c\u8005\u5f00\u59cb\u5bf9\u70f7\u57fa\u5364\u5316\u7269\u7684\u53ef\u884c\u6027\u8fdb\u884c\u4e86\u7814\u7a76\u3002\u4ee4\u4eba\u6ee1\u610f\u7684\u662f\uff0c\u4ee3\u8868\u6027\u7684\u4ef2\u70f7\u57fa\u5364\u5316\u7269\u4ea7\u726936<\/strong>–38<\/strong>\uff0c\u53ef\u5728\u4f18\u5316\u7684\u53cd\u5e94\u6761\u4ef6\u4e0b\u987a\u5229\u8fdb\u884c\u3002\u6b64\u5916\uff0c\u53d4\u4e01\u57fa\u6eb4\u5316\u7269\uff0839<\/strong>\uff09\u4e5f\u53ef\u7528\u4e8e\u6b64\u53cd\u5e94\u3002<\/p>\n

\"\"<\/a><\/p>\n

\"\"<\/a><\/p>\n

\u968f\u540e\uff0c\u4f5c\u8005\u5bf9\u82ef\u4e59\u70ef\u7684\u5e95\u7269\u8303\u56f4\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u6269\u5c55\uff08Table 3\uff09\u3002\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0c\u8be5\u53cd\u5e94\u4e0d\u53d7\u7535\u5b50\u6548\u5e94\u548c\u5b9a\u4f4d\u6548\u5e94\u7684\u5f71\u54cd\uff0c\u5747\u53ef\u83b7\u5f97\u76f8\u5e94\u03b1<\/em>-\u53d6\u4ee3\u4ea7\u726940<\/strong>–65<\/strong>\u3002\u540c\u65f6\uff0c\u4f4d\u963b\u8f83\u5927\u7684\u03b1<\/em>,\u03b2<\/em>-\u4e8c\u53d6\u4ee3\u82ef\u4e59\u70ef\u5e95\u7269\u4e5f\u53ef\u4ee5\u4e2d\u7b49\u6536\u7387\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u726966<\/strong>\u3002\u4f46\u662f\uff0c\u03b1<\/em>,\u03b2<\/em>-\u975e\u53d6\u4ee3\u82ef\u4e59\u70ef\u884d\u751f\u7269\uff0c\u4ec5\u83b7\u5f97\u4e2d\u7b49\u6536\u7387\u7684\u4ea7\u726967<\/strong>–74<\/strong>\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u787c\u9178\u916f\u57fa\u56e2\uff0870<\/strong>\uff09\u4e5f\u53ef\u4fdd\u6301\u5b8c\u6574\u7684\u6784\u578b\uff0c\u4e3a\u540e\u671f\u4fee\u9970\u63d0\u4f9b\u4e86\u591a\u79cd\u53ef\u80fd\u3002\u7136\u800c\uff0c\u8102\u65cf\u70ef\u70c3\u548c\u73af\u72b6\u82ef\u4e59\u70ef\uff0c\u5747\u4e0e\u8be5\u4f53\u7cfb\u4e0d\u517c\u5bb9\u3002<\/p>\n

\"\"<\/a><\/p>\n

\"\"<\/a><\/p>\n

\u7d27\u63a5\u7740\uff0c\u4f5c\u8005\u5c06\u5e95\u7269\u8303\u56f4\u6269\u5c55\u5230\u66f4\u5177\u6311\u6218\u6027\u7684\u7f3a\u7535\u5b50\u7684\u5421\u5576\u57fa\u5364\u5316\u7269\uff08Table 4\uff09\u3002\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0c\u5177\u6709\u786b\u4ee3\u544b\u5583\u57fa\u6216\u5421\u5576\u57fa\u7684\u70ef\u70c3\u5747\u53ef\u4ee5\u4e2d\u7b49\u6536\u7387\u83b7\u5f97\u6240\u9700\u7684\u4ea7\u726975<\/strong>\u548c76<\/strong>\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8be5\u53cd\u5e94\u8fd8\u53ef\u4e0e\u5176\u5b83\u7684\u5421\u5576\u57fa\u5364\u5316\u7269\u5e95\u7269\u53cd\u5e94\uff0c\u4ece\u800c\u4ee5\u826f\u597d\u7684\u6536\u7387\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u726977<\/strong>–81<\/strong>\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u4ea7\u726978<\/strong>\u7684\u5355\u6676X-\u5c04\u7ebf\u7ed3\u6784\u5206\u6790\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u7ed3\u6784\u7684\u6b63\u786e\u6027\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u4e3a\u4e86\u8fdb\u4e00\u6b65\u8bc1\u660e\u8be5\u53cd\u5e94\u7684\u5e95\u7269\u8303\u56f4\u7684\u5e7f\u6cdb\u6027\uff0c\u4f5c\u8005\u9009\u62e9\u4f7f\u7528\u53cd\u5e94\u6d3b\u6027\u66f4\u4f4e\u7684\u82b3\u57fa\u6c2f\u5316\u7269\uff08Table 5\uff09\u3002\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0c\u4e00\u4e9b\u66f4\u4e3a\u5ec9\u4ef7\u7684\u7f3a\u7535\u5b50\u7684\uff08\u6742\uff09\u82b3\u57fa\u6c2f\u5316\u7269\u5747\u53ef\u53d1\u751f\u7fb0\u57fa\u5316\u53cd\u5e94\uff0c\u4ece\u800c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u7269\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u4e3a\u4e86\u8fdb\u4e00\u6b65\u4e86\u89e3\u53cd\u5e94\u7684\u673a\u7406\uff0c\u4f5c\u8005\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u5bf9\u7167\u5b9e\u9a8c\uff08Scheme 2\uff09\u3002\u9996\u5148\uff0c\u5728\u6807\u51c6\u6761\u4ef6\u4e0b\uff0c\u4f53\u7cfb\u4e0d\u5b58\u5728\u82b3\u57fa\u5364\u5316\u7269\u65f6\uff0c\u83b7\u5f97\u7fa7\u57fa\u5316\u4ea7\u726983<\/strong>\u548c84<\/strong>\uff0c\u4ece\u800c\u8868\u660e\u5728\u8be5\u53cd\u5e94\u6761\u4ef6\u4e0b\u53ef\u80fd\u4f1a\u751f\u6210CO2<\/sub>\u81ea\u7531\u57fa\u9634\u79bb\u5b50\uff08Scheme 2a, 2b\uff09\u3002\u5f53\u8fdb\u884c\u81ea\u7531\u57fa\u949f\u5b9e\u9a8c\u65f6\uff0c\u83b7\u5f97\u5f00\u73af\u4ea7\u726985<\/strong>\uff0c\u8868\u660e\u8be5\u53cd\u5e94\u53ef\u80fd\u751f\u6210\u82c4\u57fa\u81ea\u7531\u57fa\uff08Scheme 2c\uff09\u3002\u800c\u901a\u8fc7\u540c\u4f4d\u7d20\u6807\u8bb0\u5b9e\u9a8c\u548c\u4f7f\u7528\u919b\u4f5c\u4e3a\u4eb2\u7535\u8bd5\u5242\u7684\u5bf9\u7167\u5b9e\u9a8c\uff08Scheme 2d, 2e\uff09\uff0c\u95f4\u63a5\u8868\u660e\u53ef\u80fd\u5b58\u5728\u82c4\u57fa\u9634\u79bb\u5b50\u4e2d\u95f4\u4f53\u3002\u6b64\u5916\uff0c\u4e3a\u4e86\u786e\u5b9a\u4ea7\u7269\u7684\u7fa7\u57fa\u6765\u6e90\uff0c\u4f5c\u8005\u4f7f\u752813<\/sup>CO2<\/sub>\uff0899\uff0513<\/sup>C\uff09\u6c14\u4f53\uff0c\u6700\u7ec8\u5728\u4ea7\u7269\u7684\u7fa7\u57fa\u4e2d\u53d1\u73b074\uff0513<\/sup>C\uff08Scheme 2f\uff09\u3002\u6700\u540e\uff0c\u8be5\u53cd\u5e94\u53ef\u4ee5\u8f7b\u677e\u6269\u5927\u81f35 mmol\uff0c\u800c\u4ea7\u7269\u7684\u6536\u7387\u6ca1\u6709\u660e\u663e\u964d\u4f4e\uff08Scheme 2g\uff09\u3002<\/p>\n

\"\"<\/a><\/p>\n

\"\"<\/a><\/p>\n

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\"\"<\/a><\/p>\n

\u603b\u7ed3<\/h4>\n

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\u672c\u6587\u7248\u6743\u5c5e\u4e8e\u00a0Chem-Station\u5316\u5b66\u7a7a\u95f4<\/a>\uff0c<\/strong>\u00a0\u6b22\u8fce\u70b9\u51fb\u6309\u94ae\u5206\u4eab\uff0c\u672a\u7ecf\u8bb8\u53ef\uff0c\u8c22\u7edd\u8f6c\u8f7d\uff01<\/p>\n","protected":false},"excerpt":{"rendered":"\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749 \u5bfc\u8bfb \u8fd1\u65e5\uff0c\u4e2d\u79d1\u9662\uff08\u798f\u5efa\u7269\u8d28\u7ed3\u6784\u7814\u7a76\u6240\uff09\u674e\u7eb2\u6559\u6388\u8bfe\u9898\u7ec4\u5728\u7f8e\u56fd\u5316\u5b66\u5b66\u4f1a\u6742\u5fd7\uff08Journal of the American Chemical Society\uff09\u53d1\u8868\u8bba\u6587\uff0c\u9996\u6b21\u62a5\u9053\u4e86\u5728\u53ef\u89c1\u5149\u4fc3\u8fdb\u4e0b\uff0c\u5b9e\u73b0\u82ef\u4e59\u70ef\u5316\u5408\u7269\u4e0eCO2\u3001\u82b3\u57fa\u5364\u5316\u7269\u7684\u533a\u57df\u9009\u62e9\u6027\u8fd8\u539f\u7fb0\u57fa\u5316\u53cd\u5e94\u3002\u8be5\u53cd\u5e94\u5177\u6709\u5e7f\u6cdb\u7684\u5e95\u7269\u8303\u56f4\uff0c\u5982\u5421\u5576\u57fa\u5364\u5316\u7269\u3001\u70f7\u57fa\u5364\u5316\u7269\u3001\u82b3\u57fa\u7898\u5316\u7269\u3001\u6eb4\u5316\u7269\uff0c\u751a\u81f3\u6c2f\u5316\u7269\u5747\u4e0e\u53cd\u5e94\u4f53\u7cfb\u517c\u5bb9\u3002\u8be5\u7b56\u7565\u4f7f\u7528\u82b3\u57fa\u5364\u5316\u7269\u4f5c\u4e3a\u81ea\u7531\u57fa\u6e90\uff0c\u4e8c\u6c27\u5316\u78b3\u4f5c\u4e3a\u7fb0\u57fa\u6e90\uff0c\u901a\u8fc7\u5149\u50ac\u5316\uff0c\u5b9e\u73b0Meerwein\u82b3\u57fa\u5316\u53cd\u5e94\u3002 Visible-Light-Driven Reductive Carboarylation of Styrenes with CO2 and Aryl Halides Hao Wang, Yuzhen Gao, Chunlin Zhou, and Gang Li J. Am. Chem. Soc. 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6\uff09\u3002\u800c\u5bf9\u5176\u5b83HAT\u50ac\u5316\u5242\u7b5b\u9009\u540e\uff0cDABCO\u5177\u6709\u8f83\u9ad8\u7684\u50ac\u5316\u6d3b\u6027\uff08entries 7-10\uff09\u3002\u8fd9\u4e9b\u7ed3\u679c\u53ef\u80fd\u8868\u660e\uff0cHCO2K\/DABCO\u7684\u7ed3\u5408\u4f5c\u4e3a\u8be5\u8fd8\u539f\u7fb0\u57fa\u5316\u53cd\u5e94\u4e2d\u6709\u6548\u7684\u7535\u5b50\u4f9b\u4f53\u3002\u6b64\u5916\uff0cK2CO3\u5bf9\u4e8e\u8be5\u53cd\u5e94\u4ec5\u7a0d\u6709\u76ca\u5904\uff08entry 11\uff09\uff0c\u800c\u5176\u4ed6\u78b1\uff08\u5982Na2CO3\u548cCs2CO3\uff09\u4e5f\u540c\u6837\u6709\u6548\uff08entries 12-13\uff09\u3002\u6700\u540e\uff0c\u4f5c\u8005\u4e5f\u5bf9\u6eb6\u5242\u8fdb\u884c\u7b5b\u9009\uff08DMF\u3001DMA\uff09\uff0c\u53d1\u73b0DMSO\u4f5c\u4e3a\u6700\u4f73\u6eb6\u5242\uff08entries 14-15\uff09\u3002 \u5728\u83b7\u5f97\u4e0a\u8ff0\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u540e\uff0c\u4f5c\u8005\u56fa\u5b9a1,1-\u4e8c\u82ef\u4e59\u70ef\uff0c\u5f00\u59cb\u5bf9\u5404\u79cd\u82b3\u57fa\u7898\u5316\u7269\u548c\u6eb4\u5316\u7269\u4ee5\u53ca\u4e00\u4e9b\u5177\u6709\u4ee3\u8868\u6027\u7684\u70f7\u57fa\u5364\u5316\u7269\u8fdb\u884c\u4e86\u6269\u5c55\uff08Table 2\uff09\u3002\u9996\u5148\uff0c\u4f7f\u7528\u5ec9\u4ef7\u7684\u6eb4\u82ef\u4ec5\u6bd4\u7898\u82ef\u83b7\u5f97\u4ea7\u72691\u7684\u6536\u7387\u7a0d\u5dee\u4e9b\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5728\u8be5\u53cd\u5e94\u4f53\u7cfb\u4e2d\u4e0d\u53d7\u7535\u5b50\u6548\u5e94\u7684\u5f71\u54cd\uff0c\u5747\u53ef\u83b7\u5f97\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u72692–33\uff0c\u5982\u7ed9\u7535\u5b50\u57fa\uff08\u7532\u57fa\u3001\u7532\u6c27\u57fa\u3001\u7532\u786b\u57fa\u7b49\uff09\uff0c\u5438\u7535\u5b50\u57fa\uff08\u6c1f\u3001\u6c2f\u4ee3\u3001\u787c\u9178\u916f\u3001\u4e09\u6c1f\u7532\u57fa\u3001\u7fb0\u57fa\u3001\u6c30\u57fa\u7b49\uff09\u3002\u4f46\u662f\uff0c\u4e00\u4e9b\u5e26\u6709\u7ed9\u7535\u5b50\u57fa\u56e2\u7684\u5e95\u7269\uff08\u5982\u4ea7\u72692–5\u7684\u5364\u5316\u7269\uff09\uff0c\u82b3\u57fa\u7898\u5316\u7269\u7684\u6536\u7387\u9ad8\u4e8e\u82b3\u57fa\u6eb4\u5316\u7269\u3002\u540c\u6837\uff0c\u5bf9\u4e8e\u67d0\u4e9b\u5177\u6709\u5438\u7535\u5b50\u57fa\u56e2\u7684\u5e95\u7269\uff0c\u5982\u4ea7\u726925\u300128\u548c32\u7684\u6eb4\u5316\u7269\uff0c\u82b3\u57fa\u6eb4\u5316\u7269\u7684\u6536\u7387\u9ad8\u4e8e\u82b3\u57fa\u7898\u5316\u7269\u3002\u800c\u4e14\uff0c\u90bb\u4f4d\u53d6\u4ee3\u7684\u82b3\u57fa\u5364\u5316\u7269\u901a\u5e38\u6bd4\u95f4\u4f4d\u548c\u5bf9\u4f4d\u53d6\u4ee3\u7684\u7684\u4ea7\u7269\u6536\u7387\u504f\u4f4e\uff0c\u5982\u4ea7\u72695–7\u300112–14\u548c28–30\u3002\u6b64\u5916\uff0c\u7898\u4ee3\u8418\uff0834\uff09\u548c\u6eb4\u4ee3\u8418\uff0835\uff09\u4e5f\u4e0e\u4f53\u7cfb\u517c\u5bb9\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5e26\u6709\u6c2f\u6216\u787c\u9178\u916f\u57fa\u56e2\u7684\u82b3\u57fa\u7898\u5316\u7269\/\u6eb4\u5316\u7269\u5e95\u7269\u4e5f\u53ef\u4e0e\u4f53\u7cfb\u517c\u5bb9\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u726915–18\uff0c\u4e3a\u8fdb\u4e00\u6b65\u884d\u751f\u5316\u63d0\u4f9b\u4e86\u591a\u79cd\u53ef\u80fd\u3002\u968f\u540e\uff0c\u4f5c\u8005\u5f00\u59cb\u5bf9\u70f7\u57fa\u5364\u5316\u7269\u7684\u53ef\u884c\u6027\u8fdb\u884c\u4e86\u7814\u7a76\u3002\u4ee4\u4eba\u6ee1\u610f\u7684\u662f\uff0c\u4ee3\u8868\u6027\u7684\u4ef2\u70f7\u57fa\u5364\u5316\u7269\u4ea7\u726936–38\uff0c\u53ef\u5728\u4f18\u5316\u7684\u53cd\u5e94\u6761\u4ef6\u4e0b\u987a\u5229\u8fdb\u884c\u3002\u6b64\u5916\uff0c\u53d4\u4e01\u57fa\u6eb4\u5316\u7269\uff0839\uff09\u4e5f\u53ef\u7528\u4e8e\u6b64\u53cd\u5e94\u3002 \u968f\u540e\uff0c\u4f5c\u8005\u5bf9\u82ef\u4e59\u70ef\u7684\u5e95\u7269\u8303\u56f4\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u6269\u5c55\uff08Table 3\uff09\u3002\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0c\u8be5\u53cd\u5e94\u4e0d\u53d7\u7535\u5b50\u6548\u5e94\u548c\u5b9a\u4f4d\u6548\u5e94\u7684\u5f71\u54cd\uff0c\u5747\u53ef\u83b7\u5f97\u76f8\u5e94\u03b1-\u53d6\u4ee3\u4ea7\u726940–65\u3002\u540c\u65f6\uff0c\u4f4d\u963b\u8f83\u5927\u7684\u03b1,\u03b2-\u4e8c\u53d6\u4ee3\u82ef\u4e59\u70ef\u5e95\u7269\u4e5f\u53ef\u4ee5\u4e2d\u7b49\u6536\u7387\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u726966\u3002\u4f46\u662f\uff0c\u03b1,\u03b2-\u975e\u53d6\u4ee3\u82ef\u4e59\u70ef\u884d\u751f\u7269\uff0c\u4ec5\u83b7\u5f97\u4e2d\u7b49\u6536\u7387\u7684\u4ea7\u726967–74\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u787c\u9178\u916f\u57fa\u56e2\uff0870\uff09\u4e5f\u53ef\u4fdd\u6301\u5b8c\u6574\u7684\u6784\u578b\uff0c\u4e3a\u540e\u671f\u4fee\u9970\u63d0\u4f9b\u4e86\u591a\u79cd\u53ef\u80fd\u3002\u7136\u800c\uff0c\u8102\u65cf\u70ef\u70c3\u548c\u73af\u72b6\u82ef\u4e59\u70ef\uff0c\u5747\u4e0e\u8be5\u4f53\u7cfb\u4e0d\u517c\u5bb9\u3002 \u7d27\u63a5\u7740\uff0c\u4f5c\u8005\u5c06\u5e95\u7269\u8303\u56f4\u6269\u5c55\u5230\u66f4\u5177\u6311\u6218\u6027\u7684\u7f3a\u7535\u5b50\u7684\u5421\u5576\u57fa\u5364\u5316\u7269\uff08Table 4\uff09\u3002\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0c\u5177\u6709\u786b\u4ee3\u544b\u5583\u57fa\u6216\u5421\u5576\u57fa\u7684\u70ef\u70c3\u5747\u53ef\u4ee5\u4e2d\u7b49\u6536\u7387\u83b7\u5f97\u6240\u9700\u7684\u4ea7\u726975\u548c76\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8be5\u53cd\u5e94\u8fd8\u53ef\u4e0e\u5176\u5b83\u7684\u5421\u5576\u57fa\u5364\u5316\u7269\u5e95\u7269\u53cd\u5e94\uff0c\u4ece\u800c\u4ee5\u826f\u597d\u7684\u6536\u7387\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u726977–81\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u4ea7\u726978\u7684\u5355\u6676X-\u5c04\u7ebf\u7ed3\u6784\u5206\u6790\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u7ed3\u6784\u7684\u6b63\u786e\u6027\u3002 \u4e3a\u4e86\u8fdb\u4e00\u6b65\u8bc1\u660e\u8be5\u53cd\u5e94\u7684\u5e95\u7269\u8303\u56f4\u7684\u5e7f\u6cdb\u6027\uff0c\u4f5c\u8005\u9009\u62e9\u4f7f\u7528\u53cd\u5e94\u6d3b\u6027\u66f4\u4f4e\u7684\u82b3\u57fa\u6c2f\u5316\u7269\uff08Table 5\uff09\u3002\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0c\u4e00\u4e9b\u66f4\u4e3a\u5ec9\u4ef7\u7684\u7f3a\u7535\u5b50\u7684\uff08\u6742\uff09\u82b3\u57fa\u6c2f\u5316\u7269\u5747\u53ef\u53d1\u751f\u7fb0\u57fa\u5316\u53cd\u5e94\uff0c\u4ece\u800c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u7269\u3002 \u4e3a\u4e86\u8fdb\u4e00\u6b65\u4e86\u89e3\u53cd\u5e94\u7684\u673a\u7406\uff0c\u4f5c\u8005\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u5bf9\u7167\u5b9e\u9a8c\uff08Scheme 2\uff09\u3002\u9996\u5148\uff0c\u5728\u6807\u51c6\u6761\u4ef6\u4e0b\uff0c\u4f53\u7cfb\u4e0d\u5b58\u5728\u82b3\u57fa\u5364\u5316\u7269\u65f6\uff0c\u83b7\u5f97\u7fa7\u57fa\u5316\u4ea7\u726983\u548c84\uff0c\u4ece\u800c\u8868\u660e\u5728\u8be5\u53cd\u5e94\u6761\u4ef6\u4e0b\u53ef\u80fd\u4f1a\u751f\u6210CO2\u81ea\u7531\u57fa\u9634\u79bb\u5b50\uff08Scheme 2a, 2b\uff09\u3002\u5f53\u8fdb\u884c\u81ea\u7531\u57fa\u949f\u5b9e\u9a8c\u65f6\uff0c\u83b7\u5f97\u5f00\u73af\u4ea7\u726985\uff0c\u8868\u660e\u8be5\u53cd\u5e94\u53ef\u80fd\u751f\u6210\u82c4\u57fa\u81ea\u7531\u57fa\uff08Scheme 2c\uff09\u3002\u800c\u901a\u8fc7\u540c\u4f4d\u7d20\u6807\u8bb0\u5b9e\u9a8c\u548c\u4f7f\u7528\u919b\u4f5c\u4e3a\u4eb2\u7535\u8bd5\u5242\u7684\u5bf9\u7167\u5b9e\u9a8c\uff08Scheme 2d, 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