{"id":18099,"date":"2018-03-06T06:34:22","date_gmt":"2018-03-05T22:34:22","guid":{"rendered":"\/\/www.gsbet888.com\/?p=18099"},"modified":"2019-08-02T18:51:55","modified_gmt":"2019-08-02T10:51:55","slug":"%e5%85%89%e5%82%ac%e5%8c%96%e4%b8%8e%e9%93%9c%e5%82%ac%e5%8c%96%e5%8d%8f%e5%90%8c%e5%82%ac%e5%8c%96%e6%b4%bb%e6%80%a7%e9%85%af%e8%84%b1%e7%be%a7csp3-n%e9%94%ae%e5%81%b6%e8%81%94%e5%8f%8d%e5%ba%94","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2018\/03\/%e5%85%89%e5%82%ac%e5%8c%96%e4%b8%8e%e9%93%9c%e5%82%ac%e5%8c%96%e5%8d%8f%e5%90%8c%e5%82%ac%e5%8c%96%e6%b4%bb%e6%80%a7%e9%85%af%e8%84%b1%e7%be%a7csp3-n%e9%94%ae%e5%81%b6%e8%81%94%e5%8f%8d%e5%ba%94.html","title":{"rendered":"\u5149\u50ac\u5316\u4e0e\u94dc\u50ac\u5316\u534f\u540c\u50ac\u5316\u6d3b\u6027\u916f\u8131\u7fa7C(sp3)-N\u952e\u5076\u8054\u53cd\u5e94"},"content":{"rendered":"<p>\u672c\u6587\u6295\u7a3f\u4f5c\u8005 \u9f50\u85e9<\/p>\n<p>\u78b3\u6c2e\u952e\u5f62\u6210\u53cd\u5e94\u662f\u6709\u673a\u5316\u5b66\u53ca\u5236\u836f\u5de5\u4e1a\u4e2d\u6700\u4e3a\u91cd\u8981\u7684\u8f6c\u5316\u4e4b\u4e00\u3002\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u78b3\u6c2e\u952e\u5f62\u6210\u53cd\u5e94\u662f\u6784\u5efa\u78b3\u6c2e\u952e\u7684\u91cd\u8981\u65b9\u6cd5\u4e4b\u4e00\uff0c\u6700\u7ecf\u5178\u7684\u53cd\u5e94\u662fUllmann\u53cd\u5e94\u548cBuchwald-Hartwig\u53cd\u5e94\u3002\u7136\u800c\u8fd9\u4e24\u7c7b\u53cd\u5e94\u4e3b\u8981\u7528\u4e8e\u82b3\u57fa\u4eb2\u7535\u8bd5\u5242\u4e0e\u80fa\u7684\u5076\u8054\uff0c\u70f7\u57fa\u4eb2\u7535\u8bd5\u5242\u4e0e\u80fa\u7684\u5076\u8054\u53cd\u5e94\u7684\u6210\u529f\u62a5\u9053\u4e0d\u591a\uff0c\u800c\u4e14\u4eb2\u6838\u8bd5\u5242\u80fa\u4ec5\u9650\u4e8e\u5494\u5511\u548c\u9170\u80fa\uff0c\u56e0\u6b64\u53d1\u5c55\u66f4\u4e3a\u666e\u9002\u7684\u78b3\u6c2e\u952e\u5f62\u6210\u65b9\u6cd5\u662f\u6781\u4e3a\u91cd\u8981\u7684\u3002Baran\u7b49<sup>1<\/sup>\u5229\u7528\u6c27\u5316\u8fd8\u539f\u6d3b\u6027\u916f\u4f5c\u4e3a\u4eb2\u7535\u8bd5\u5242\u53d1\u5c55\u4e86\u4e00\u7cfb\u5217\u8131\u7fa7\u78b3\u78b3\u5076\u8054\u53cd\u5e94\uff0c\u6b64\u540e\u8be5\u6d3b\u6027\u916f\u4e5f\u88abLi<sup>2a<\/sup>, Glorius<sup>2b<\/sup>, Aggarwal<sup>2c<\/sup>, Fu<sup>2d<\/sup>\u7b49\u8bfe\u9898\u7ec4\u76f8\u7ee7\u5e94\u7528\u4e8e\u78b3\u787c\u952e\u7684\u6784\u5efa\uff0c\u78b3\u6c2e\u952e\u5f62\u6210\u53cd\u5e94\u8fd8\u6ca1\u6709\u76f8\u5173\u62a5\u9053\u3002Hu\u7b49\u5229\u7528\u5149\u50ac\u5316\u4e0e\u94dc\u50ac\u5316\u53cc\u50ac\u5316\u4f53\u7cfb\u5b9e\u73b0\u4e86\u70f7\u57fa\u6d3b\u6027\u916f\u4e0e\u80fa\u7684\u8131\u7fa7\u5076\u8054\u53cd\u5e94\uff0c\u8be5\u8f6c\u5316\u53ef\u7528\u4e8e\u4e00\u7ea7\u3001\u4e8c\u7ea7\u7fa7\u9178\u7684\u8f6c\u5316\uff0c\u53ef\u7528\u4e8e\u6c28\u57fa\u9178\u3001\u5929\u7136\u4ea7\u7269\u4ee5\u53ca\u836f\u7269\u5206\u5b50\u7684\u5b98\u80fd\u5316\u3002<\/p>\n<blockquote><p>Decarboxylative C(sp3)\u2013N cross-coupling via synergetic photoredox and copper catalysis.<\/p>\n<p>Mao, R.; Frey, A.; Balon, J.; Hu, X.,<\/p>\n<p><em>Nature Catalysis <\/em><strong>2018,<\/strong><em>1<\/em> (2), 120-126. <a href=\"https:\/\/www.nature.com\/articles\/s41929-017-0023-z\">doi:10.1038\/s41929-017-0023-z<\/a><\/p><\/blockquote>\n<h4><strong>1.\u53cd\u5e94\u6761\u4ef6\u7684\u63a2\u7d22<\/strong><\/h4>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/2.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-18101 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/2.png\" alt=\"\" width=\"890\" height=\"291\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/2.png 890w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/2-300x98.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/2-768x251.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/2-680x222.png 680w\" sizes=\"(max-width: 890px) 100vw, 890px\" \/><\/a><\/p>\n<p style=\"text-align: center\">\u56fe1. \u53cd\u5e94\u6700\u521d\u5c1d\u8bd5<\/p>\n<p>\u4f5c\u8005\u9996\u5148\u5229\u7528Baran\u5728\u78b3\u78b3\u5076\u8054\u53cd\u5e94\u4e2d\u7684\u7c7b\u4f3c\u6761\u4ef6\uff0c\u5c1d\u8bd5\u4e86\u8be5\u53cd\u5e94\uff0c\u4ea7\u7269\u4e2d\u6ca1\u6709\u8131\u7fa7\u5f62\u6210\u80fa\u5316\u7684\u4ea7\u7269\uff0c\u4e3b\u8981\u7f29\u5408\u6210\u9170\u80fa\u3002Fu\u7b49<sup>3<\/sup>\u5229\u7528\u5149\u50ac\u5316\u4e0e\u94dc\u50ac\u5316\u534f\u540c\u50ac\u5316\u7684\u7b56\u7565\u5b9e\u73b0\u4e86\u6d3b\u6027\u916f\u4e0e\u7aef\u7094\u7684\u8131\u7fa7\u5076\u8054\u53cd\u5e94\u3002\u4f5c\u8005\u4ee5\u73af\u5df1\u57fa\u6d3b\u6027\u916f\u4e0e\u82ef\u80fa\u4e3a\u5e95\u7269\u7b5b\u9009\u4e86\u5149\u50ac\u5316\u5242\uff0cRu(bpy)<sub>3<\/sub>(BF<sub>6<\/sub>)<sub>2<\/sub>\u662f\u6700\u5408\u9002\u7684\u50ac\u5316\u5242\uff0c\u5c1d\u8bd5\u4e86\u94c1\u3001\u94b4\u3001\u954d\u3001\u94dc\u50ac\u5316\u5242\uff0c\u53d1\u73b0\u53ea\u6709\u94dc\u50ac\u5316\u5242\u80fd\u5f97\u5230\u4e00\u5b9a\u91cf\u7684\u80fa\u5316\u7684\u4ea7\u7269\uff0c\u5e76\u4e14\u53d1\u73b0\u4e00\u4ef7\u94dc\u76d0\u66f4\u6709\u5229\u4e8e\u8be5\u8f6c\u5316\u7684\u8fdb\u884c\uff0c\u6eb4\u5316\u4e9a\u94dc\u53cd\u5e94\u6548\u679c\u66f4\u597d\u3002\u6b64\u5916\uff0c\u4f5c\u8005\u8fdb\u884c\u4e86\u5927\u91cf\u7684\u914d\u4f53\u7b5b\u9009\u5de5\u4f5c\uff0c\u6700\u5f00\u59cb\u4ee51,3-\u4e8c\u916e\u7c7b\u5316\u5408\u7269\u4e3a\u53cd\u5e94\u7684\u914d\u4f53\uff0c\u53d1\u73b0\u5927\u4f4d\u963b\u76842,2,6,6-\u56db\u7532\u57fa-3,5-\u5e9a\u4e8c\u916e\uff08L1\uff09\u5728\u8fd9\u4e00\u7c7b\u914d\u4f53\u4e2d\u6548\u679c\u6700\u597d\u3002\u7136\u540e\u4f5c\u8005\u8f6c\u5411\u5229\u7528\u8349\u9170\u4e59\u9178\u6216\u8349\u9170\u80fa\u8fd9\u7c7b\u5316\u5408\u7269\u4f5c\u4e3a\u914d\u4f53\uff0c\u8fd9\u7c7b\u5316\u5408\u7269\u66fe\u5728\u94dc\u50ac\u5316\u6c2f\u4ee3\u82b3\u70c3\u7684\u80fa\u5316\u53cd\u5e94\u4e2d\u7528\u4f5c\u914d\u4f53\uff0c\u53d1\u73b0L2\u53ef\u4ee5\u5927\u5e45\u63d0\u5347\u53cd\u5e94\u7684\u4ea7\u7387\uff0c\u7136\u540e\u4f5c\u8005\u5c06L2\u4e2d\u7684\u90bb\u4f4d\u7532\u57fa\u66ff\u6362\u6210\u7532\u6c27\u57fa\uff0c\u53cd\u5e94\u6548\u679c\u8fbe\u5230\u6700\u4f18\uff0c\u5373L3\u4e3a\u6700\u4f18\u914d\u4f53\uff0c\u4f5c\u8005\u8ba4\u4e3a\u90bb\u4f4d\u7684\u53cc\u53d6\u4ee3\u52a0\u5f3a\u4e86\u914d\u4f53\u7684\u4f4d\u963b\u6709\u5229\u4e8e\u78b3\u6c2e\u952e\u7684\u8fd8\u539f\u6d88\u9664\uff0c\u540c\u65f6\u5bcc\u7535\u5b50\u7684\u53d6\u4ee3\u57fa\u6709\u5229\u4e8e\u91d1\u5c5e\u4e2d\u95f4\u4f53\u7684\u6c27\u5316\u3002\u6700\u540e\u786e\u5b9a\u53cd\u5e94\u7684\u6700\u4f18\u6761\u4ef6\u4e3a\uff0c1 mol% Ru(bpy)<sub>3<\/sub>(BF<sub>6<\/sub>)<sub>2<\/sub>\/20 mol% CuBr\u4e3a\u50ac\u5316\u5242\uff0cblue LED\u4e3a\u5149\u6e90\uff0c5\u500d\u91cf\u4e09\u4e59\u80fa\u4e3a\u78b1\uff0c\u5ba4\u6e29\u4e0b\u4e59\u8148\u6eb6\u5242\u4e2d\u53cd\u5e9412 h\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/3.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-18102 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/3.png\" alt=\"\" width=\"786\" height=\"467\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/3.png 786w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/3-300x178.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/3-768x456.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/3-680x404.png 680w\" sizes=\"(max-width: 786px) 100vw, 786px\" \/><\/a><\/p>\n<p style=\"text-align: center\">\u56fe2. \u50ac\u5316\u5242\u7b5b\u9009<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/4.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-18103 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/4.png\" alt=\"\" width=\"643\" height=\"604\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/4.png 643w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/4-300x282.png 300w\" sizes=\"(max-width: 643px) 100vw, 643px\" \/><\/a><\/p>\n<p style=\"text-align: center\">\u56fe3. \u914d\u4f53\u7b5b\u9009<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/5.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-18104 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/5.png\" alt=\"\" width=\"609\" height=\"574\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/5.png 609w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/5-300x283.png 300w\" sizes=\"(max-width: 609px) 100vw, 609px\" \/><\/a><\/p>\n<p style=\"text-align: center\">\u56fe4. \u53cd\u5e94\u6761\u4ef6\u4f18\u5316<\/p>\n<p>&nbsp;<\/p>\n<h4><strong>2.\u5e95\u7269\u9002\u7528\u8303\u56f4\u4e0e\u5e94\u7528<\/strong><\/h4>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/6.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-18105 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/6.png\" alt=\"\" width=\"888\" height=\"428\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/6.png 888w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/6-300x145.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/6-768x370.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/6-680x328.png 680w\" sizes=\"(max-width: 888px) 100vw, 888px\" \/><\/a><\/p>\n<p style=\"text-align: center\">\u56fe5. \u82b3\u80fa\u5e95\u7269\u62d3\u5c55<\/p>\n<p>\u4f5c\u8005\u4ee5\u73af\u5df1\u57fa\u6d3b\u6027\u916f\u4e3a\u5e95\u7269\uff0c\u5728\u6700\u4f18\u6761\u4ef6\u4e0b\u9996\u5148\u8003\u5bdf\u4e86\u82b3\u80fa\u7684\u9002\u7528\u8303\u56f4\uff0c\u53d1\u73b0\u82b3\u73af\u4e0a\u90bb\u3001\u95f4\u3001\u5bf9\u90fd\u80fd\u4ee5\u8f83\u597d\u4ea7\u7387\u5f97\u5230\u76f8\u5e94\u4ea7\u7269\uff0c\u5728\u4f9b\u7535\u5b50\u5e95\u7269\u4e2d\u53d1\u73b0\uff0c\u4f9b\u7535\u5b50\u80fd\u529b\u8d8a\u5f3a\u7684\u53d6\u4ee3\u57fa\uff0c\u53cd\u5e94\u6548\u679c\u66f4\u597d\uff0c\u4ea7\u7387\u66f4\u9ad8\u3002\u5364\u7d20F\u3001Cl\u3001Br\uff0c\u751a\u81f3\u6d3b\u6027\u5f88\u9ad8\u5bb9\u6613\u4ea7\u751f\u81ea\u7531\u57fa\u7684\u7898\u4ee3\u82b3\u70c3\u90fd\u80fd\u5f88\u597d\u7684\u517c\u5bb9\uff0c\u66f4\u591a\u6837\u66f4\u5177\u5e94\u7528\u4ef7\u503c\u7684\u5b98\u80fd\u56e2\uff0c\u5982\u8148\u57fa\u3001\u88ab\u4fdd\u62a4\u7684\u919b\u57fa\u3001\u4e59\u7094\u57fa\u3001\u70ef\u57fa\u3001\u4e59\u9170\u57fa\u3001\u7532\u9170\u6c27\u57fa\u3001\u4e09\u6c1f\u7532\u57fa\u90fd\u80fd\u5f88\u597d\u5730\u9002\u7528\u8fd9\u4e00\u8f6c\u5316\u3002\u5176\u4ed6\u6c2e\u4eb2\u6838\u8bd5\u5242\uff0c1-\u6c28\u57fa\u5421\u5576\uff0c\u6c28\u57fa\u55b9\u5549\uff0c\u82ef\u78fa\u9170\u80fa\uff0c\u82b3\u7532\u9170\u80fa\uff0c\u82ef\u57fa\u8132\u7b49\u90fd\u80fd\u517c\u5bb9\uff0c\u76f8\u5bf9\u4ea7\u7387\u8f83\u4f4e\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/7.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-18106 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/7.png\" alt=\"\" width=\"893\" height=\"318\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/7.png 893w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/7-300x107.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/7-768x273.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/03\/7-680x242.png 680w\" sizes=\"(max-width: 893px) 100vw, 893px\" \/><\/a><\/p>\n<p style=\"text-align: center\">\u56fe6. 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J. et al. Practical Ni-catalyzed aryl\u2013alkyl cross-coupling of secondary redox-active esters.<em>\u00a0J. Am. Chem. Soc.<\/em><strong>2016<\/strong>, <em>138<\/em>, 2174\u20132177.<a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/jacs.6b00250\"><strong>DOI:\u00a0<\/strong>10.1021\/jacs.6b00250.<\/a>(b) Qin, T. et al. A general alkyl\u2013alkyl cross-coupling enabled by redox-active esters and alkylzinc reagents.\u00a0<em>Science<\/em>\u00a0.<strong>2016<\/strong>, <em>352<\/em>, 801\u2013805.<a href=\"http:\/\/science.sciencemag.org\/content\/352\/6287\/801\">DOI: 10.1126\/science.aaf6123.<\/a> (c) Toriyama, F. et al. Redox-active esters in Fe-catalyzed C\u2013C coupling.\u00a0<em>J. Am. Chem. Soc.\u00a0<\/em><strong>2016<\/strong>,\u00a0<em>138<\/em>, 11132\u201311135.<a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/jacs.6b07172\">DOI:<strong>\u00a0<\/strong>10.1021\/jacs.6b07172.<\/a><\/li>\n<li>(a) Hu, D.; Wang, L.; Li, P. <em>Org.\u00a0Lett. <\/em><strong>2017,<\/strong><em>19<\/em>, 2770. <a href=\"https:\/\/pubs.acs.org\/doi\/abs\/10.1021\/acs.orglett.7b01181?journalCode=orlef7&amp;quickLinkVolume=19&amp;quickLinkPage=2770&amp;selectedTab=citation&amp;volume=19\">DOI:10.1021\/acs.orglett.7b01181.<\/a> (b) Candish,\u00a0L.;\u00a0Teders,\u00a0M.;\u00a0Glorius,\u00a0F.\u00a0<em>J. Am. Chem. Soc.<\/em>\u00a0<strong>2017<\/strong>,\u00a0<em>139<\/em>,\u00a07440-7443. <a href=\"https:\/\/pubs.acs.org\/doi\/abs\/10.1021\/jacs.7b03127?journalCode=jacsat&amp;quickLinkVolume=139&amp;quickLinkPage=7440&amp;selectedTab=citation&amp;volume=139\">DOI:<strong>\u00a0<\/strong>10.1021\/jacs.7b03127.<\/a>(c) Fawcett,\u00a0A.;\u00a0Pradeilles,\u00a0J.;\u00a0Wang,\u00a0Y.;\u00a0Mutsuga,\u00a0T.;\u00a0Myers,\u00a0E. L.;\u00a0Aggarwal,\u00a0V. K.\u00a0<em>Science.<\/em>\u00a0<strong>2017<\/strong>,\u00a0<em>357<\/em>,\u00a0283.<a href=\"http:\/\/science.sciencemag.org\/content\/357\/6348\/283\">DOI: 10.1126\/science.aan3679.<\/a> (d) Cheng, W.-M.; Shang, R.; Zhao, B.; Xing, W.-L.; Fu, Y. <em>Org. Lett. <\/em><strong>2017,<\/strong><em>19<\/em>, 4291. <a href=\"https:\/\/pubs.acs.org\/doi\/abs\/10.1021\/acs.orglett.7b01950?journalCode=orlef7&amp;quickLinkVolume=19&amp;quickLinkPage=4291&amp;selectedTab=citation&amp;volume=19\"><strong>DOI:\u00a0<\/strong>10.1021\/acs.orglett.7b01950.<\/a><\/li>\n<li>Zhang, H., Zhang, P., Jiang, M., Yang, H. &amp; Fu, H. Merging photoredox with copper catalysis: decarboxylativealkynylation of \u03b1-amino acid derivatives. <em>Org. Lett.<\/em><strong>2017<\/strong>, <em>19<\/em>, 1016\u20131019 (2017).<a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/acs.orglett.6b03888\"><strong>DOI:\u00a0<\/strong>10.1021\/acs.orglett.6b03888.<\/a><\/li>\n<\/ol>\n<p>\u672c\u6587\u7248\u6743\u5c5e\u4e8e<strong>\u00a0<a href=\"\/\/www.gsbet888.com\/\">Chem-Station\u5316\u5b66\u7a7a\u95f4<\/a>\uff0c<\/strong> \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\u6295\u7a3f\u4f5c\u8005 \u9f50\u85e9 \u78b3\u6c2e\u952e\u5f62\u6210\u53cd\u5e94\u662f\u6709\u673a\u5316\u5b66\u53ca\u5236\u836f\u5de5\u4e1a\u4e2d\u6700\u4e3a\u91cd\u8981\u7684\u8f6c\u5316\u4e4b\u4e00\u3002\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u78b3\u6c2e\u952e\u5f62\u6210\u53cd\u5e94\u662f\u6784\u5efa\u78b3\u6c2e\u952e\u7684\u91cd\u8981\u65b9\u6cd5\u4e4b\u4e00\uff0c\u6700\u7ecf\u5178\u7684\u53cd\u5e94\u662fUllmann\u53cd\u5e94\u548cBuchwald-Hartwig\u53cd\u5e94\u3002\u7136\u800c\u8fd9\u4e24\u7c7b\u53cd\u5e94\u4e3b\u8981\u7528\u4e8e\u82b3\u57fa\u4eb2\u7535\u8bd5\u5242\u4e0e\u80fa\u7684\u5076\u8054\uff0c\u70f7\u57fa\u4eb2\u7535\u8bd5\u5242\u4e0e\u80fa\u7684\u5076\u8054\u53cd\u5e94\u7684\u6210\u529f\u62a5\u9053\u4e0d\u591a\uff0c\u800c\u4e14\u4eb2\u6838\u8bd5\u5242\u80fa\u4ec5\u9650\u4e8e\u5494\u5511\u548c\u9170\u80fa\uff0c\u56e0\u6b64\u53d1\u5c55\u66f4\u4e3a\u666e\u9002\u7684\u78b3\u6c2e\u952e\u5f62\u6210\u65b9\u6cd5\u662f\u6781\u4e3a\u91cd\u8981\u7684\u3002Baran\u7b491\u5229\u7528\u6c27\u5316\u8fd8\u539f\u6d3b\u6027\u916f\u4f5c\u4e3a\u4eb2\u7535\u8bd5\u5242\u53d1\u5c55\u4e86\u4e00\u7cfb\u5217\u8131\u7fa7\u78b3\u78b3\u5076\u8054\u53cd\u5e94\uff0c\u6b64\u540e\u8be5\u6d3b\u6027\u916f\u4e5f\u88abLi2a, Glorius2b, Aggarwal2c, Fu2d\u7b49\u8bfe\u9898\u7ec4\u76f8\u7ee7\u5e94\u7528\u4e8e\u78b3\u787c\u952e\u7684\u6784\u5efa\uff0c\u78b3\u6c2e\u952e\u5f62\u6210\u53cd\u5e94\u8fd8\u6ca1\u6709\u76f8\u5173\u62a5\u9053\u3002Hu\u7b49\u5229\u7528\u5149\u50ac\u5316\u4e0e\u94dc\u50ac\u5316\u53cc\u50ac\u5316\u4f53\u7cfb\u5b9e\u73b0\u4e86\u70f7\u57fa\u6d3b\u6027\u916f\u4e0e\u80fa\u7684\u8131\u7fa7\u5076\u8054\u53cd\u5e94\uff0c\u8be5\u8f6c\u5316\u53ef\u7528\u4e8e\u4e00\u7ea7\u3001\u4e8c\u7ea7\u7fa7\u9178\u7684\u8f6c\u5316\uff0c\u53ef\u7528\u4e8e\u6c28\u57fa\u9178\u3001\u5929\u7136\u4ea7\u7269\u4ee5\u53ca\u836f\u7269\u5206\u5b50\u7684\u5b98\u80fd\u5316\u3002 Decarboxylative C(sp3)\u2013N cross-coupling via synergetic photoredox and copper catalysis. Mao, R.; Frey, A.; Balon, J.; Hu, X., Nature Catalysis 2018,1 (2), 120-126. doi:10.1038\/s41929-017-0023-z 1.\u53cd\u5e94\u6761\u4ef6\u7684\u63a2\u7d22 \u56fe1. \u53cd\u5e94\u6700\u521d\u5c1d\u8bd5 \u4f5c\u8005\u9996\u5148\u5229\u7528Baran\u5728\u78b3\u78b3\u5076\u8054\u53cd\u5e94\u4e2d\u7684\u7c7b\u4f3c\u6761\u4ef6\uff0c\u5c1d\u8bd5\u4e86\u8be5\u53cd\u5e94\uff0c\u4ea7\u7269\u4e2d\u6ca1\u6709\u8131\u7fa7\u5f62\u6210\u80fa\u5316\u7684\u4ea7\u7269\uff0c\u4e3b\u8981\u7f29\u5408\u6210\u9170\u80fa\u3002Fu\u7b493\u5229\u7528\u5149\u50ac\u5316\u4e0e\u94dc\u50ac\u5316\u534f\u540c\u50ac\u5316\u7684\u7b56\u7565\u5b9e\u73b0\u4e86\u6d3b\u6027\u916f\u4e0e\u7aef\u7094\u7684\u8131\u7fa7\u5076\u8054\u53cd\u5e94\u3002\u4f5c\u8005\u4ee5\u73af\u5df1\u57fa\u6d3b\u6027\u916f\u4e0e\u82ef\u80fa\u4e3a\u5e95\u7269\u7b5b\u9009\u4e86\u5149\u50ac\u5316\u5242\uff0cRu(bpy)3(BF6)2\u662f\u6700\u5408\u9002\u7684\u50ac\u5316\u5242\uff0c\u5c1d\u8bd5\u4e86\u94c1\u3001\u94b4\u3001\u954d\u3001\u94dc\u50ac\u5316\u5242\uff0c\u53d1\u73b0\u53ea\u6709\u94dc\u50ac\u5316\u5242\u80fd\u5f97\u5230\u4e00\u5b9a\u91cf\u7684\u80fa\u5316\u7684\u4ea7\u7269\uff0c\u5e76\u4e14\u53d1\u73b0\u4e00\u4ef7\u94dc\u76d0\u66f4\u6709\u5229\u4e8e\u8be5\u8f6c\u5316\u7684\u8fdb\u884c\uff0c\u6eb4\u5316\u4e9a\u94dc\u53cd\u5e94\u6548\u679c\u66f4\u597d\u3002\u6b64\u5916\uff0c\u4f5c\u8005\u8fdb\u884c\u4e86\u5927\u91cf\u7684\u914d\u4f53\u7b5b\u9009\u5de5\u4f5c\uff0c\u6700\u5f00\u59cb\u4ee51,3-\u4e8c\u916e\u7c7b\u5316\u5408\u7269\u4e3a\u53cd\u5e94\u7684\u914d\u4f53\uff0c\u53d1\u73b0\u5927\u4f4d\u963b\u76842,2,6,6-\u56db\u7532\u57fa-3,5-\u5e9a\u4e8c\u916e\uff08L1\uff09\u5728\u8fd9\u4e00\u7c7b\u914d\u4f53\u4e2d\u6548\u679c\u6700\u597d\u3002\u7136\u540e\u4f5c\u8005\u8f6c\u5411\u5229\u7528\u8349\u9170\u4e59\u9178\u6216\u8349\u9170\u80fa\u8fd9\u7c7b\u5316\u5408\u7269\u4f5c\u4e3a\u914d\u4f53\uff0c\u8fd9\u7c7b\u5316\u5408\u7269\u66fe\u5728\u94dc\u50ac\u5316\u6c2f\u4ee3\u82b3\u70c3\u7684\u80fa\u5316\u53cd\u5e94\u4e2d\u7528\u4f5c\u914d\u4f53\uff0c\u53d1\u73b0L2\u53ef\u4ee5\u5927\u5e45\u63d0\u5347\u53cd\u5e94\u7684\u4ea7\u7387\uff0c\u7136\u540e\u4f5c\u8005\u5c06L2\u4e2d\u7684\u90bb\u4f4d\u7532\u57fa\u66ff\u6362\u6210\u7532\u6c27\u57fa\uff0c\u53cd\u5e94\u6548\u679c\u8fbe\u5230\u6700\u4f18\uff0c\u5373L3\u4e3a\u6700\u4f18\u914d\u4f53\uff0c\u4f5c\u8005\u8ba4\u4e3a\u90bb\u4f4d\u7684\u53cc\u53d6\u4ee3\u52a0\u5f3a\u4e86\u914d\u4f53\u7684\u4f4d\u963b\u6709\u5229\u4e8e\u78b3\u6c2e\u952e\u7684\u8fd8\u539f\u6d88\u9664\uff0c\u540c\u65f6\u5bcc\u7535\u5b50\u7684\u53d6\u4ee3\u57fa\u6709\u5229\u4e8e\u91d1\u5c5e\u4e2d\u95f4\u4f53\u7684\u6c27\u5316\u3002\u6700\u540e\u786e\u5b9a\u53cd\u5e94\u7684\u6700\u4f18\u6761\u4ef6\u4e3a\uff0c1 mol% Ru(bpy)3(BF6)2\/20 mol% CuBr\u4e3a\u50ac\u5316\u5242\uff0cblue LED\u4e3a\u5149\u6e90\uff0c5\u500d\u91cf\u4e09\u4e59\u80fa\u4e3a\u78b1\uff0c\u5ba4\u6e29\u4e0b\u4e59\u8148\u6eb6\u5242\u4e2d\u53cd\u5e9412 h\u3002 \u56fe2. \u50ac\u5316\u5242\u7b5b\u9009 \u56fe3. \u914d\u4f53\u7b5b\u9009 \u56fe4. \u53cd\u5e94\u6761\u4ef6\u4f18\u5316 &nbsp; 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\u7ed3\u8bba \u5149\u50ac\u5316\u4e0e\u94dc\u50ac\u5316\u7684\u534f\u540c\u50ac\u5316\u80fd\u591f\u5b9e\u73b0\u70f7\u57fa\u6d3b\u6027\u916f\u4e0e\u80fa\u7684\u8131\u7fa7\u80fa\u5316\u53cd\u5e94\uff0c\u8fd9\u4e00\u8f6c\u5316\u6781\u5927\u5730\u62d3\u5c55\u4e86\u91d1\u5c5e\u50ac\u5316Sp3\u78b3\u6c2e\u952e\u5076\u8054\u53cd\u5e94\u3002\u7531\u4e8e\u70f7\u57fa\u7fa7\u9178\u4e0e\u70f7\u57fa\u5364\u4ee3\u70c3\u76f8\u6bd4\uff0c\u5728\u53ef\u83b7\u5f97\u6027\u3001\u7a33\u5b9a\u6027\u3001\u6bd2\u6027\u4e0a\u7684\u4f18\u52bf\uff0c\u8fd9\u4e00\u65b9\u6cd5\u53ca\u5176\u7b56\u7565\u5c06\u6709\u671b\u5728\u80fa\u7684\u5408\u6210\u4e2d\u6709\u5e7f\u6cdb\u7684\u5e94\u7528\u3002\u6b64\u5916\uff0c\u7531\u4e8e\u5149\u50ac\u5316\u4e0e\u91d1\u5c5e\u50ac\u5316\u7684\u4e32\u8054\u5728\u8131\u7fa7\u78b3\u78b3\u5076\u8054\u53cd\u5e94\u4e2d\u5e94\u7528\u6700\u5e7f\u7684\u662f\u954d\u50ac\u5316\u5242\u4e0e\u5149\u50ac\u5316\u7684\u7ed3\u5408\uff0c\u56e0\u6b64\u8fd9\u4e00\u94dc\u50ac\u5316\u4e0e\u5149\u50ac\u5316\u7684\u534f\u540c\u50ac\u5316\u8131\u7fa7\u78b3\u6c2e\u5076\u8054\u53cd\u5e94\u4e30\u5bcc\u4e86\u8fd9\u4e00\u7b56\u7565\u3002 &nbsp; \u53c2\u8003\u6587\u732e (a)Cornella, J. et al. Practical Ni-catalyzed aryl\u2013alkyl cross-coupling of secondary redox-active esters.\u00a0J. Am. Chem. Soc.2016, 138, 2174\u20132177.DOI:\u00a010.1021\/jacs.6b00250.(b) Qin, T. et al. A general alkyl\u2013alkyl cross-coupling enabled by redox-active esters and alkylzinc reagents.\u00a0Science\u00a0.2016, 352, 801\u2013805.DOI: 10.1126\/science.aaf6123. (c) Toriyama, F. et al. 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