{"id":22041,"date":"2018-12-21T06:29:54","date_gmt":"2018-12-20T22:29:54","guid":{"rendered":"\/\/www.gsbet888.com\/?p=22041"},"modified":"2019-08-02T18:50:57","modified_gmt":"2019-08-02T10:50:57","slug":"angew-chem-int-ed-%e9%98%b3%e7%a6%bb%e5%ad%90%e4%b8%89%e6%a0%b8pd%e5%82%ac%e5%8c%96%e7%9a%84%e9%80%89%e6%8b%a9%e6%80%a7c-i%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\/2018\/12\/angew-chem-int-ed-%e9%98%b3%e7%a6%bb%e5%ad%90%e4%b8%89%e6%a0%b8pd%e5%82%ac%e5%8c%96%e7%9a%84%e9%80%89%e6%8b%a9%e6%80%a7c-i%e9%94%ae%e5%81%b6%e8%81%94%e5%8f%8d%e5%ba%94.html","title":{"rendered":"Angew. Chem., Int. Ed. \u9633\u79bb\u5b50\u4e09\u6838Pd\u50ac\u5316\u7684\u9009\u62e9\u6027C-I\u952e\u5076\u8054\u53cd\u5e94"},"content":{"rendered":"<p><b>\u6807\u9898\u8bba\u6587\u62a5\u9053\u4e86\u82b3\u57fa\u7898\u7684\u9009\u62e9\u6027\u4ea4\u53c9\u5076\u8054\u3002\u4f5c\u8005\u901a\u8fc7\u4f7f\u7528\u65b0\u578b\u9633\u79bb\u5b50\u4e09\u6838\u94af\u50ac\u5316\u5242\uff0c\u53ef\u4ee5\u518dC-Br\u548cC-Cl\u952e\u5b58\u5728\u4e0b\u9009\u62e9\u6027\u5730\u5bf9<span lang=\"EN-CA\">C\u2013I\u8fdb\u884c\u5076\u8054\u53cd\u5e94<\/span>\u3002<\/b><\/p>\n<h4 class=\"1\"><span lang=\"EN-US\">C\u2013I\u952e\u7684\u9009\u62e9\u6027\u5076\u8054\u53cd\u5e94<\/span><\/h4>\n<p class=\"a\">\u5982\u679c\u53ef\u4ee5\u9009\u62e9\u6027\u5bf9\u5982\u7898\uff0c\u6eb4\u6216\u6c2f\u4f4d\u70b9\u8fdb\u884c\u5076\u8054\u53cd\u5e94\uff0c\u5219\u53ef\u4ee5\u5feb\u901f\u5408\u6210\u9ad8\u5ea6\u5b98\u80fd\u5316\u7684\u5316\u5408\u7269\u3002\u4ee3\u8868\u6027\u7684\u4f8b\u5b50\u4e4b\u4e00\uff0c<a href=\"\/\/www.gsbet888.com\/chemists\/2014\/11\/gregory-c-fu.html\">Fu<\/a>\u7b49\u4eba\u901a\u8fc7\u4f7f\u7528\u4e0d\u540c\u7684Pd\u7684\u50ac\u5316\u5242\u5b9e\u73b0\u4e86\u4e0eC-Cl\u4e0eC-OTf\u7684\u9009\u62e9\u6027\u5076\u8054\u53cd\u5e94<sup><span lang=\"EN-US\">[1]<\/span><\/sup><span lang=\"EN-US\">(\u56fe<\/span><span lang=\"EN-US\">1A)<\/span>\u3002\u53e6\u4e00\u65b9\u9762\uff0c<span lang=\"EN-US\">C\u2013I\u4e0e<\/span><span lang=\"EN-US\">C\u2013Br\u7684\u9009\u62e9\u6027\u5076\u8054\u8fd8\u672a\u80fd\u591f\u89e3\u51b3<\/span>\u3002<span lang=\"EN-US\">Knochel\u7b49\u4eba\u4f7f\u7528\u7f3a\u7535\u5b50\u7684\u78f7\u914d\u4f53\u8fdb\u884cNegishi\u5076\u8054\uff0c\u867d\u7136\u5728<\/span><span lang=\"EN-US\">C\u2013Br<\/span>\u5b58\u5728\u4e0b\u5b9e\u73b0\u4e86<span lang=\"EN-US\">C\u2013I\u7684\u9009\u62e9\u6027\u5076\u8054<\/span>\u3001\u4f46\u662f\u53ea\u6709\u4ee5\u5bf9\u6eb4\u82ef\u4e3a\u5e95\u7269\u7684\u4e24\u4e2a\u5e94\u7528\u4f8b\uff0c\u8fd8\u4e0d\u80fd\u8bf4\u53ef\u4ee5\u4f5c\u4e3a\u4e00\u822c\u7684\u5e94\u7528\u65b9\u6cd5\u4f7f\u7528<sup><span lang=\"EN-US\">[2a]<\/span><\/sup><span lang=\"EN-US\">(\u56fe<\/span><span lang=\"EN-US\">1B)<\/span>\u3002\u56e0\u6b64\uff0c\u4f7f\u7528<span lang=\"EN-US\">Pd(0)<\/span>\u50ac\u5316\u5242\u8fdb\u884c\u7684<span lang=\"EN-US\">C\u2013I<\/span>\u9009\u62e9\u6027\u5076\u8054\u5bf9\u5e95\u7269\u9650\u5236\u5f88\u5927\u662f\u4e00\u4e2a\u5de8\u5927\u7684\u5c40\u9650\u3002\u57fa\u4e8e\u6b64\uff0c<span lang=\"EN-US\"><a href=\"\/\/www.gsbet888.com\/chemists\/2018\/12\/gary-a-molander-2.html\">Molander<\/a>\u7b49\u4eba\u4f7f\u7528<\/span><span lang=\"EN-US\">Ni\/Photoredox\u50ac\u5316\u4f53\u7cfb\uff0c\u5b9e\u73b0\u4e86\u5728<\/span><span lang=\"EN-US\">C<\/span>\u2013<span lang=\"EN-US\">Br<\/span>\u5b58\u5728\u4e0b\u8fdb\u884c<span lang=\"EN-US\">C\u2013I\u9009\u62e9\u6027\u70f7\u57fa\u5316\u5076\u8054\u53cd\u5e94\uff0c\u7136\u800c\u8be5\u53cd\u5e94\u4e0d\u9002\u7528\u4e8e<\/span><span lang=\"EN-US\">sp<sup>2<\/sup><\/span>\u4eb2\u6838\u5242<sup><span lang=\"EN-US\">[2b]<\/span><\/sup><span lang=\"EN-US\">(\u56fe<\/span><span lang=\"EN-US\">1B)<\/span>\u3002<\/p>\n<p>\u3000\u53e6\u4e00\u65b9\u9762\uff0c\u672c\u6b21\u4ecb\u7ecd\u7684\u8bba\u6587\u7684\u4f5c\u8005<span lang=\"EN-US\">Schoenebeck\u7b49\u4eba\uff0c\u5f00\u53d1\u51fa\u4e86<\/span><span lang=\"EN-US\">Pd(I)\u4e8c\u805a\u4f53<\/span><b><span lang=\"EN-US\">1<\/span><\/b>\u3001\u5e76\u4e14\u4f7f\u7528\u8be5\u4e8c\u805a\u4f53\u50ac\u5316\u5242\u5b9e\u73b0\u4e86<span lang=\"EN-US\">C\u2013Cl, C\u2013Br\u4ee5\u53ca<\/span><span lang=\"EN-US\">C\u2013OTf\u952e\u7684\u9009\u62e9\u6027\u5076\u8054\u53cd\u5e94<\/span><sup><span lang=\"EN-US\">[3]<\/span><\/sup><span lang=\"EN-US\">(\u56fe<\/span><span lang=\"EN-US\">1C)<\/span>\u3002\u800c\u8fd9\u6b21\uff0c\u4ed6\u4eec\u53c8\u4f7f\u7528\u9633\u79bb\u5b50\u4e09\u6838Pd\u50ac\u5316\u5242\u3001\u5728<a href=\"\/\/www.gsbet888.com\/reactions\/2014\/01\/%e6%a0%bc%e5%88%a9%e9%9b%85%e5%8f%8d%e5%ba%94%ef%bc%88%e6%a0%bc%e6%b0%8f%e5%8f%8d%e5%ba%94%ef%bc%89grignard-reaction.html\"><span lang=\"EN-US\">Grignard \u8bd5\u5242<\/span><\/a>\u4f5c\u7528\u4e0b\uff0c\u5b9e\u73b0\u4e86<span lang=\"EN-US\">C\u2013I\u952e\u7684\u9ad8\u4ea7\u7387<\/span>\u30fb\u9ad8\u9009\u62e9\u6027\u5076\u8054\u53cd\u5e94<span lang=\"EN-US\">(\u56fe<\/span><span lang=\"EN-US\">1D)<\/span>\u3002<\/p>\n<div id=\"attachment_61627\" class=\"wp-caption aligncenter\">\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-22043 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/12\/2018-12-18_00-48-01-680x477.png\" alt=\"\" width=\"680\" height=\"477\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/12\/2018-12-18_00-48-01-680x477.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/12\/2018-12-18_00-48-01-300x210.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/12\/2018-12-18_00-48-01-768x539.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/12\/2018-12-18_00-48-01.png 840w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/p>\n<p class=\"wp-caption-text\">\u56fe1. (A), (B), (C) \u5e38\u89c4\u591a\u5364\u4ee3\u82b3\u70c3\u7684\u533a\u57df\u9009\u62e9\u6027\u5076\u8054 (D) \u672c\u6b21\u4ecb\u7ecd\u7684\u53cd\u5e94<\/p>\n<\/div>\n<blockquote><p><strong>\u201cC\u2013I Selective Cross-Coupling Enabled by a Cationic Pd Trimer\u201d<\/strong><\/p>\n<p>Diehl, C. J.; Scattolin, T.; Englert, U.; Schoenebeck, F. <em>Angew. Chem., Int. Ed.<\/em><strong>2018,\u00a0<\/strong>Accepted Article<\/p>\n<p>DOI: <a href=\"https:\/\/doi.org\/10.1002\/anie.201811380\">10.1002\/anie.201811380<\/a><\/p><\/blockquote>\n<h4>\u8bba\u6587\u4f5c\u8005\u4ecb\u7ecd<\/h4>\n<p>\u7814\u7a76\u8005\uff1a<a href=\"http:\/\/www.schoenebeck.oc.rwth-aachen.de\/\">Franziska Schoenebeck<\/a><\/p>\n<p>\u5c65\u5386\uff1a<br \/>\n2001\u20132004 BSc, Technical University Berlin, Germany and University of Strathclyde, Glasgow, UK<br \/>\n2004\u20132008 Ph.D, WestCHEM Research School, Glasgow, UK (Prof. John A. Murphy)<br \/>\n2008\u20132010 Posdoc, University of California, Los Angeles, USA (Prof.K. N. Houk)<br \/>\n2010\u20132013 Assistant Professor, ETH Z\u00fcrich, Switzerland<br \/>\n2013\u2013 Professor (W2), RWTH Aachen University, Germany<\/p>\n<p>\u7814\u7a76\u5185\u5bb9\uff1a\u8ba1\u7b97\u5316\u5b66\u4e0e\u4f7f\u7528\u8ba1\u7b97\u5316\u5b66\u8fdb\u884c\u7684\u50ac\u5316\u5242\u8bbe\u8ba1<\/p>\n<h4 class=\"1\">\u8bba\u6587\u6982\u8981<\/h4>\n<p class=\"a\">\u672c\u53cd\u5e94\u4e2d\u4f7f\u7528\u7684\u4e09\u6838<span lang=\"EN-US\">Pd\u50ac\u5316\u5242<\/span><b><span lang=\"EN-US\">2<\/span><\/b>\u3001\u53ef\u4ee5\u901a\u8fc7\u5728<span lang=\"EN-US\">Pd(I)\u4e8c\u805a\u4f53<\/span><b><span lang=\"EN-US\">1<\/span><\/b>\u4e2d\u52a0\u5165<span lang=\"EN-US\">4<\/span>\u5f53\u91cf\u4e8c\u82ef\u57fa\u81a6\u5236\u5907\uff0c\u4ea7\u7387\u8fbe\u523099%<span lang=\"EN-US\">(\u56fe<\/span><span lang=\"EN-US\">2A)<\/span>\u3002\u5f97\u5230\u7684\u50ac\u5316\u5242<b><span lang=\"EN-US\">2<\/span><\/b>\u5bf9\u7a7a\u6c14\uff0c\u6c34\u7a33\u5b9a\u3002\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u7814\u7a76\u4e86\u5e95\u72691-\u6eb4-4-\u7898\u82ef\uff08<strong>3a<\/strong>\uff09\u548cPhMgCl\uff08<strong>4a<\/strong>\uff09\u5728\u50ac\u5316\u5242<strong>2<\/strong>\u4f5c\u7528\u4e0b\u4e0e\u5176\u4ed6\u4e00\u822cPd\u50ac\u5316\u5242\u4f5c\u7528\u4e0b\u7684\u9009\u62e9\u6027\u5076\u8054\u53cd\u5e94\u6d3b\u6027<span lang=\"EN-US\">(\u56fe<\/span><span lang=\"EN-US\">2B)<\/span>\u3002\u4f5c\u8005\u53d1\u73b0\u3001<span lang=\"EN-US\">Pd(0)\u50ac\u5316\u5242\u4ee5\u53ca<\/span><span lang=\"EN-US\">Pd(I)\u4e8c\u805a\u4f53\u50ac\u5316\u5242<\/span><b><span lang=\"EN-US\">1<\/span><\/b>\u7684\u53cd\u5e94\uff0c\u5076\u8054\u540c\u65f6\u80fd\u53d1\u751f\u5728C-Br\u4e0eC-I\u952e\u4e0a\uff0c\u526f\u4ea7\u7269\u4e3a\u53cc\u5076\u8054\u5316\u5408\u7269<b><span lang=\"EN-US\">6<\/span><\/b>\u3002<\/p>\n<p class=\"a\">\u53e6\u4e00\u65b9\u9762\u3001\u4f7f\u7528\u4e09\u6838<span lang=\"EN-US\">Pd\u50ac\u5316\u5242<\/span><b><span lang=\"EN-US\">2<\/span><\/b>\u7684\u53cd\u5e94\u4e2d\u3001\u5b8c\u5168\u6ca1\u6709\u526f\u4ea7\u7269<b><span lang=\"EN-US\">6<\/span><\/b>\u7684\u5f62\u6210\uff0c\u53cd\u5e94\u9009\u62e9\u6027\u7684\u53d1\u751f\u5728<span lang=\"EN-US\">C\u2013I\u952e\u4e0a\u751f\u6210\u4e864-\u6eb4\u8054\u82ef<\/span><span lang=\"EN-US\">(<b>5a<\/b>)\uff0c\u4ea7\u7387\u9ad8\u8fbe<\/span><span lang=\"EN-US\">88%<\/span>\u3002\u53e6\u5916\uff0c\u5373\u4f7f\u5728in-situ\u4e0b\u751f\u6210\u50ac\u5316\u5242<strong>2<\/strong>\u8fdb\u884c\u7684\u50ac\u5316\u53cd\u5e94\uff0c\u4e5f\u663e\u793a\u4e86\u540c\u6837\u7684\u53cd\u5e94\u6d3b\u6027\u3002\u8be5\u53cd\u5e94\u6761\u4ef6\u5e95\u7269\u9002\u7528\u6027\u5e7f\u3001\u5373\u4f7f\u4f7f\u7528\u90bb\u4f4d\u4e8c\u53d6\u4ee3\u5316\u5408\u7269<span lang=\"EN-US\">(<b>5e<\/b>)\uff0c\u4e5f\u80fd\u4ee5\u9ad8\u4ea7\u7387\u8fdb\u884c\u53cd\u5e94<\/span><span lang=\"EN-US\">(\u56fe<\/span><span lang=\"EN-US\">2C)<\/span>\u3002\u53e6\u5916\uff0c\u4f7f\u7528\u70f7\u57fa\u53d6\u4ee3\u7684<span lang=\"EN-US\">Grignard\u8bd5\u5242<\/span><span lang=\"EN-US\">(<b>5g<\/b>, <b>5h<\/b>)\u4e5f\u80fd\u8fdb\u884c\u53cd\u5e94<\/span>\u3002\u901a\u8fc7EPR\u89e3\u6790\u4f5c\u8005\u786e\u8ba4\u5728\u8be5\u53cd\u5e94\u4e2d\u4e0d\u5b58\u5728\u957f\u5bff\u547d\u7684\u81ea\u7531\u57fa\u3002\u540c\u65f6\uff0c\u901a\u8fc7<span lang=\"EN-US\">DFT\u8ba1\u7b97\uff0c\u4e09\u6838\u50ac\u5316\u5242<\/span><b><span lang=\"EN-US\">2<\/span><\/b>\u662f\u76f4\u63a5\u8fdb\u884c\u6c27\u5316\u52a0\u6210\u50ac\u5316\u7684\u53cd\u5e94\u3002<\/p>\n<div id=\"attachment_61628\" class=\"wp-caption aligncenter\">\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-22044 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/12\/2018-12-18_00-50-23-680x417.png\" alt=\"\" width=\"680\" height=\"417\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2018\/12\/2018-12-18_00-50-23-680x417.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/12\/2018-12-18_00-50-23-300x184.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/12\/2018-12-18_00-50-23-768x471.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/12\/2018-12-18_00-50-23-233x144.png 233w, https:\/\/assets.www.gsbet888.com\/uploads\/2018\/12\/2018-12-18_00-50-23.png 992w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/p>\n<p class=\"wp-caption-text\">\u56fe2. (A) \u4e09\u6838Pd\u50ac\u5316\u5242<strong>2<\/strong>\u7684\u5408\u6210 (B) \u5404Pd\u50ac\u5316\u5242\u7684\u53cd\u5e94\u6027 (C) \u5e95\u7269\u9002\u7528\u8303\u56f4<\/p>\n<\/div>\n<p>\u7efc\u4e0a\u6240\u8ff0\uff0c\u5728\u4e09\u6838<span lang=\"EN-US\">Pd\u50ac\u5316\u5242\u50ac\u5316\u4e0b\uff0c\u4f5c\u8005\u5b9e\u73b0\u4e86C-I\u9009\u62e9\u6027\u5076\u8054\u53cd\u5e94\u3002\u540c\u65f6\u50ac\u5316\u5242\u7684\u7a33\u5b9a\u6027\u5f88\u9ad8\uff0c\u4eca\u540e\u5f88\u53ef\u80fd\u4f5c\u4e3a\u5364\u4ee3\u5316\u5408\u7269\u7684\u5076\u8054\u53cd\u5e94\u50ac\u5316\u5242\u88ab\u5e7f\u6cdb\u4f7f\u7528\u3002<\/span><\/p>\n<h4>\u53c2\u8003\u6587\u732e<\/h4>\n<ol>\n<li>Littke, A. F.; Dai, C.; Fu, G. C. <em>J.<\/em>\u00a0<em>Am. Chem. Soc.<\/em><strong>2000<\/strong>, <em>122<\/em>, 4020 DOI: <a href=\"https:\/\/doi.org\/10.1021\/ja0002058\">10.1021\/ja0002058<\/a><\/li>\n<li>(a) Betzemeier, B.; Knochel, P. <em>Angew.<\/em>\u00a0<em>Chem., Int. Ed. Engl. <\/em><strong>1997, <\/strong><em>36, <\/em>2623 DOI: <a href=\"https:\/\/doi.org\/10.1002\/anie.199726231\">10.1002\/anie.199726231<\/a>(b) Lin, K.; Wiles, R. J.; Kelly, C. B.; Davies, G. H. M.; Molander, G. A. <em>ACS Catal. <\/em><strong>2017, <\/strong><em>7<\/em>, 5129. DOI: <a href=\"https:\/\/doi.org\/10.1021\/acscatal.7b01773\">10.1021\/acscatal.7b01773<\/a><\/li>\n<li>Keaveney, S. T.; Kundu, G.; Schoenebeck, F. <em>Angew.<\/em>\u00a0<em>Chem., Int. Ed. <\/em><strong>2018<\/strong>, <em>57<\/em>, 12573. DOI: <a href=\"https:\/\/doi.org\/10.1002\/anie.201808386\">10.1002\/anie.201808386<\/a><\/li>\n<\/ol>\n<p><strong>\u672c\u6587\u7248\u6743\u5c5e\u4e8e\u00a0<a href=\"\/\/www.gsbet888.com\/\">Chem-Station\u5316\u5b66\u7a7a\u95f4<\/a>\uff0c \u6b22\u8fce\u70b9\u51fb\u6309\u94ae\u5206\u4eab\uff0c\u672a\u7ecf\u8bb8\u53ef\uff0c\u8c22\u7edd\u8f6c\u8f7d\uff01<\/strong> <\/p>\n","protected":false},"excerpt":{"rendered":"\u6807\u9898\u8bba\u6587\u62a5\u9053\u4e86\u82b3\u57fa\u7898\u7684\u9009\u62e9\u6027\u4ea4\u53c9\u5076\u8054\u3002\u4f5c\u8005\u901a\u8fc7\u4f7f\u7528\u65b0\u578b\u9633\u79bb\u5b50\u4e09\u6838\u94af\u50ac\u5316\u5242\uff0c\u53ef\u4ee5\u518dC-Br\u548cC-Cl\u952e\u5b58\u5728\u4e0b\u9009\u62e9\u6027\u5730\u5bf9C\u2013I\u8fdb\u884c\u5076\u8054\u53cd\u5e94\u3002 C\u2013I\u952e\u7684\u9009\u62e9\u6027\u5076\u8054\u53cd\u5e94 \u5982\u679c\u53ef\u4ee5\u9009\u62e9\u6027\u5bf9\u5982\u7898\uff0c\u6eb4\u6216\u6c2f\u4f4d\u70b9\u8fdb\u884c\u5076\u8054\u53cd\u5e94\uff0c\u5219\u53ef\u4ee5\u5feb\u901f\u5408\u6210\u9ad8\u5ea6\u5b98\u80fd\u5316\u7684\u5316\u5408\u7269\u3002\u4ee3\u8868\u6027\u7684\u4f8b\u5b50\u4e4b\u4e00\uff0cFu\u7b49\u4eba\u901a\u8fc7\u4f7f\u7528\u4e0d\u540c\u7684Pd\u7684\u50ac\u5316\u5242\u5b9e\u73b0\u4e86\u4e0eC-Cl\u4e0eC-OTf\u7684\u9009\u62e9\u6027\u5076\u8054\u53cd\u5e94[1](\u56fe1A)\u3002\u53e6\u4e00\u65b9\u9762\uff0cC\u2013I\u4e0eC\u2013Br\u7684\u9009\u62e9\u6027\u5076\u8054\u8fd8\u672a\u80fd\u591f\u89e3\u51b3\u3002Knochel\u7b49\u4eba\u4f7f\u7528\u7f3a\u7535\u5b50\u7684\u78f7\u914d\u4f53\u8fdb\u884cNegishi\u5076\u8054\uff0c\u867d\u7136\u5728C\u2013Br\u5b58\u5728\u4e0b\u5b9e\u73b0\u4e86C\u2013I\u7684\u9009\u62e9\u6027\u5076\u8054\u3001\u4f46\u662f\u53ea\u6709\u4ee5\u5bf9\u6eb4\u82ef\u4e3a\u5e95\u7269\u7684\u4e24\u4e2a\u5e94\u7528\u4f8b\uff0c\u8fd8\u4e0d\u80fd\u8bf4\u53ef\u4ee5\u4f5c\u4e3a\u4e00\u822c\u7684\u5e94\u7528\u65b9\u6cd5\u4f7f\u7528[2a](\u56fe1B)\u3002\u56e0\u6b64\uff0c\u4f7f\u7528Pd(0)\u50ac\u5316\u5242\u8fdb\u884c\u7684C\u2013I\u9009\u62e9\u6027\u5076\u8054\u5bf9\u5e95\u7269\u9650\u5236\u5f88\u5927\u662f\u4e00\u4e2a\u5de8\u5927\u7684\u5c40\u9650\u3002\u57fa\u4e8e\u6b64\uff0cMolander\u7b49\u4eba\u4f7f\u7528Ni\/Photoredox\u50ac\u5316\u4f53\u7cfb\uff0c\u5b9e\u73b0\u4e86\u5728C\u2013Br\u5b58\u5728\u4e0b\u8fdb\u884cC\u2013I\u9009\u62e9\u6027\u70f7\u57fa\u5316\u5076\u8054\u53cd\u5e94\uff0c\u7136\u800c\u8be5\u53cd\u5e94\u4e0d\u9002\u7528\u4e8esp2\u4eb2\u6838\u5242[2b](\u56fe1B)\u3002 \u3000\u53e6\u4e00\u65b9\u9762\uff0c\u672c\u6b21\u4ecb\u7ecd\u7684\u8bba\u6587\u7684\u4f5c\u8005Schoenebeck\u7b49\u4eba\uff0c\u5f00\u53d1\u51fa\u4e86Pd(I)\u4e8c\u805a\u4f531\u3001\u5e76\u4e14\u4f7f\u7528\u8be5\u4e8c\u805a\u4f53\u50ac\u5316\u5242\u5b9e\u73b0\u4e86C\u2013Cl, C\u2013Br\u4ee5\u53caC\u2013OTf\u952e\u7684\u9009\u62e9\u6027\u5076\u8054\u53cd\u5e94[3](\u56fe1C)\u3002\u800c\u8fd9\u6b21\uff0c\u4ed6\u4eec\u53c8\u4f7f\u7528\u9633\u79bb\u5b50\u4e09\u6838Pd\u50ac\u5316\u5242\u3001\u5728Grignard \u8bd5\u5242\u4f5c\u7528\u4e0b\uff0c\u5b9e\u73b0\u4e86C\u2013I\u952e\u7684\u9ad8\u4ea7\u7387\u30fb\u9ad8\u9009\u62e9\u6027\u5076\u8054\u53cd\u5e94(\u56fe1D)\u3002 \u56fe1. (A), (B), (C) \u5e38\u89c4\u591a\u5364\u4ee3\u82b3\u70c3\u7684\u533a\u57df\u9009\u62e9\u6027\u5076\u8054 (D) \u672c\u6b21\u4ecb\u7ecd\u7684\u53cd\u5e94 \u201cC\u2013I Selective Cross-Coupling Enabled by a Cationic Pd Trimer\u201d Diehl, C. J.; Scattolin, T.; Englert, U.; Schoenebeck, F. Angew. Chem., Int. Ed.2018,\u00a0Accepted Article DOI: 10.1002\/anie.201811380 \u8bba\u6587\u4f5c\u8005\u4ecb\u7ecd \u7814\u7a76\u8005\uff1aFranziska Schoenebeck \u5c65\u5386\uff1a 2001\u20132004 BSc, Technical University Berlin, Germany and University of Strathclyde, Glasgow, UK 2004\u20132008 Ph.D, WestCHEM Research School, Glasgow, UK (Prof. John A. Murphy) 2008\u20132010 Posdoc, University of California, Los Angeles, USA (Prof.K. N. Houk) 2010\u20132013 Assistant Professor, ETH Z\u00fcrich, Switzerland 2013\u2013 Professor (W2), RWTH Aachen University, Germany \u7814\u7a76\u5185\u5bb9\uff1a\u8ba1\u7b97\u5316\u5b66\u4e0e\u4f7f\u7528\u8ba1\u7b97\u5316\u5b66\u8fdb\u884c\u7684\u50ac\u5316\u5242\u8bbe\u8ba1 \u8bba\u6587\u6982\u8981 \u672c\u53cd\u5e94\u4e2d\u4f7f\u7528\u7684\u4e09\u6838Pd\u50ac\u5316\u52422\u3001\u53ef\u4ee5\u901a\u8fc7\u5728Pd(I)\u4e8c\u805a\u4f531\u4e2d\u52a0\u51654\u5f53\u91cf\u4e8c\u82ef\u57fa\u81a6\u5236\u5907\uff0c\u4ea7\u7387\u8fbe\u523099%(\u56fe2A)\u3002\u5f97\u5230\u7684\u50ac\u5316\u52422\u5bf9\u7a7a\u6c14\uff0c\u6c34\u7a33\u5b9a\u3002\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u7814\u7a76\u4e86\u5e95\u72691-\u6eb4-4-\u7898\u82ef\uff083a\uff09\u548cPhMgCl\uff084a\uff09\u5728\u50ac\u5316\u52422\u4f5c\u7528\u4e0b\u4e0e\u5176\u4ed6\u4e00\u822cPd\u50ac\u5316\u5242\u4f5c\u7528\u4e0b\u7684\u9009\u62e9\u6027\u5076\u8054\u53cd\u5e94\u6d3b\u6027(\u56fe2B)\u3002\u4f5c\u8005\u53d1\u73b0\u3001Pd(0)\u50ac\u5316\u5242\u4ee5\u53caPd(I)\u4e8c\u805a\u4f53\u50ac\u5316\u52421\u7684\u53cd\u5e94\uff0c\u5076\u8054\u540c\u65f6\u80fd\u53d1\u751f\u5728C-Br\u4e0eC-I\u952e\u4e0a\uff0c\u526f\u4ea7\u7269\u4e3a\u53cc\u5076\u8054\u5316\u5408\u72696\u3002 \u53e6\u4e00\u65b9\u9762\u3001\u4f7f\u7528\u4e09\u6838Pd\u50ac\u5316\u52422\u7684\u53cd\u5e94\u4e2d\u3001\u5b8c\u5168\u6ca1\u6709\u526f\u4ea7\u72696\u7684\u5f62\u6210\uff0c\u53cd\u5e94\u9009\u62e9\u6027\u7684\u53d1\u751f\u5728C\u2013I\u952e\u4e0a\u751f\u6210\u4e864-\u6eb4\u8054\u82ef(5a)\uff0c\u4ea7\u7387\u9ad8\u8fbe88%\u3002\u53e6\u5916\uff0c\u5373\u4f7f\u5728in-situ\u4e0b\u751f\u6210\u50ac\u5316\u52422\u8fdb\u884c\u7684\u50ac\u5316\u53cd\u5e94\uff0c\u4e5f\u663e\u793a\u4e86\u540c\u6837\u7684\u53cd\u5e94\u6d3b\u6027\u3002\u8be5\u53cd\u5e94\u6761\u4ef6\u5e95\u7269\u9002\u7528\u6027\u5e7f\u3001\u5373\u4f7f\u4f7f\u7528\u90bb\u4f4d\u4e8c\u53d6\u4ee3\u5316\u5408\u7269(5e)\uff0c\u4e5f\u80fd\u4ee5\u9ad8\u4ea7\u7387\u8fdb\u884c\u53cd\u5e94(\u56fe2C)\u3002\u53e6\u5916\uff0c\u4f7f\u7528\u70f7\u57fa\u53d6\u4ee3\u7684Grignard\u8bd5\u5242(5g, 5h)\u4e5f\u80fd\u8fdb\u884c\u53cd\u5e94\u3002\u901a\u8fc7EPR\u89e3\u6790\u4f5c\u8005\u786e\u8ba4\u5728\u8be5\u53cd\u5e94\u4e2d\u4e0d\u5b58\u5728\u957f\u5bff\u547d\u7684\u81ea\u7531\u57fa\u3002\u540c\u65f6\uff0c\u901a\u8fc7DFT\u8ba1\u7b97\uff0c\u4e09\u6838\u50ac\u5316\u52422\u662f\u76f4\u63a5\u8fdb\u884c\u6c27\u5316\u52a0\u6210\u50ac\u5316\u7684\u53cd\u5e94\u3002 \u56fe2. (A) \u4e09\u6838Pd\u50ac\u5316\u52422\u7684\u5408\u6210 (B) \u5404Pd\u50ac\u5316\u5242\u7684\u53cd\u5e94\u6027 (C) \u5e95\u7269\u9002\u7528\u8303\u56f4 \u7efc\u4e0a\u6240\u8ff0\uff0c\u5728\u4e09\u6838Pd\u50ac\u5316\u5242\u50ac\u5316\u4e0b\uff0c\u4f5c\u8005\u5b9e\u73b0\u4e86C-I\u9009\u62e9\u6027\u5076\u8054\u53cd\u5e94\u3002\u540c\u65f6\u50ac\u5316\u5242\u7684\u7a33\u5b9a\u6027\u5f88\u9ad8\uff0c\u4eca\u540e\u5f88\u53ef\u80fd\u4f5c\u4e3a\u5364\u4ee3\u5316\u5408\u7269\u7684\u5076\u8054\u53cd\u5e94\u50ac\u5316\u5242\u88ab\u5e7f\u6cdb\u4f7f\u7528\u3002 \u53c2\u8003\u6587\u732e Littke, A. F.; Dai, C.; Fu, G. 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