{"id":24826,"date":"2019-03-21T10:14:48","date_gmt":"2019-03-21T02:14:48","guid":{"rendered":"\/\/www.gsbet888.com\/?p=24826"},"modified":"2019-03-21T10:14:48","modified_gmt":"2019-03-21T02:14:48","slug":"j-am-chem-soc-counter-anion%e5%af%bc%e5%90%91%e7%9a%84%e6%89%8b%e6%80%a7%e6%b0%a8%e5%9f%ba%e7%94%b2%e5%9f%ba%e5%8c%96","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/2019\/03\/j-am-chem-soc-counter-anion%e5%af%bc%e5%90%91%e7%9a%84%e6%89%8b%e6%80%a7%e6%b0%a8%e5%9f%ba%e7%94%b2%e5%9f%ba%e5%8c%96.html","title":{"rendered":"J. Am. Chem. Soc. Counter-Anion\u5bfc\u5411\u7684\u624b\u6027\u6c28\u57fa\u7532\u57fa\u5316"},"content":{"rendered":"<p><b>\u6700\u8fd1\uff0c\u4e2d\u5c71\u5927\u5b66\u836f\u5b66\u9662\u80e1\u6587\u6d69\u6559\u6388\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86\u901a\u8fc7\u63a7\u5236\u4e9a\u80faCounter-Anion\u6765\u63a7\u5236\u624b\u6027\u7684\u80fa\u57fa\u7532\u57fa\u5316\u65b9\u6cd5\u3002<\/b><\/p>\n<h4 class=\"1\">\u6c28\u57fa\u7532\u57fa\u5316\u4e0e\u5176\u624b\u6027\u63a7\u5236\u6cd5<\/h4>\n<p class=\"a\">\u5929\u7136\u4ea7\u7269\u4e0e\u533b\u836f\u5c0f\u5206\u5b50\u4e2d\u9891\u51fa\u7684\u300c\u6c28\u57fa\u7532\u57fa\u57fa\u56e2\u300d\u3001\u56e0\u6b64\u5f00\u53d1\u4e00\u79cd\u9ad8\u6548\u7684\u6c28\u57fa\u7532\u57fa\u5316\u65b9\u6cd5\u662f\u975e\u5e38\u6709\u4ef7\u503c\u7684\u3002\u8fc4\u4eca\u4e3a\u6b62\uff0c\u5df2\u7ecf\u62a5\u9053\u4e86\u5f88\u591a\u901a\u8fc7\u91d1\u5c5e\u50ac\u5316\u53cd\u5e94\u4e0e\u81ea\u7531\u57fa\u53cd\u5e94\u8fdb\u884c\u7684\u6c28\u57fa\u7532\u57fa\u5316\u5b9e\u4f8b<sup><span lang=\"EN-US\">[1]<\/span><\/sup>\u3002\u7136\u800c\uff0c\u50ac\u5316\u4e0d\u5bf9\u79f0\u6c28\u57fa\u7532\u57fa\u5316\u7684\u5b9e\u4f8b\u8fd8\u662f\u5f88\u6709\u9650\u3002\u5176\u4e2d\u7684\u4ee3\u8868\u6027\u5b9e\u4f8b\u6709\uff0c\u812f\u6c28\u9178\u50ac\u5316\u4e0b\u7684\u66fc\u5c3c\u5e0c\u578b\u916e\u548c\u4e9a\u80fa\u79bb\u5b50\u7684\u4e0d\u5bf9\u79f0\u6c28\u57fa\u7532\u57fa\u5316\uff08\u56fe<span lang=\"EN-US\">1A<\/span>\uff09<sup><span lang=\"EN-US\">[2a]<\/span><\/sup>\u3002\u7531\u916e\u548c\u812f\u6c28\u9178\u4ea7\u751f\u7684\u624b\u6027\u70ef\u80fa\uff08\u4eb2\u6838\u8bd5\u5242\uff09\u901a\u8fc7\u5bf9\u4f53\u7cfb\u4e2d\u751f\u6210\u7684\u4e9a\u80fa\u79bb\u5b50\uff08\u4eb2\u7535\u8bd5\u5242\uff09\u8fdb\u884c\u4eb2\u6838\u653b\u51fb\u6765\u4ea7\u751f\u624b\u6027\u4ea7\u7269\u3002\u6b64\u5916\uff0c\u5df2\u7ecf\u62a5\u9053\u4e86\u5728\u5176\u4ed6\u624b\u6027\u80fa\u50ac\u5316\u5242\u5b58\u5728\u4e0b\u4f7f\u7528\u919b<sup><span lang=\"EN-US\">[2b]<\/span><\/sup>\u548c1,3-\u4e8c\u916e\u4f5c\u4e3a\u4eb2\u6838\u8bd5\u5242<sup><span lang=\"EN-US\">[2c]<\/span><\/sup>\u7684\u7c7b\u4f3c\u7684\u4e0d\u5bf9\u79f0\u6c28\u57fa\u7532\u57fa\u5316\u53cd\u5e94\uff08\u56fe<span lang=\"EN-US\">1B<\/span>\uff09\u3002\u8fd9\u4e9b\u5b9e\u4f8b\u90fd\u662f\u5148\u5f62\u6210\u624b\u6027\u7684\u4eb2\u6838\u8bd5\u5242\u7136\u540e\u8fdb\u884c\u7684\u624b\u6027\u8bf1\u5bfc\uff0c\u56e0\u6b64\u5e95\u7269\u5c31\u5c40\u9650\u5728\u4e86\u53ef\u4ee5\u751f\u6210\u70ef\u80fa\u7684\u7fb0\u57fa\u5316\u5408\u7269\u4e0a\u3002<\/p>\n<p>\u9488\u5bf9\u4e8e\u8fd9\u4e2a\u95ee\u9898\uff0c\u4e2d\u5c71\u5927\u5b66\u7684\u80e1\u6559\u6388\u8bfe\u9898\u7ec4\u7740\u773c\u4e8e\u624b\u6027\u78f7\u9178\u50ac\u5316\u5242\u3001\u5f00\u53d1\u51fa\u4e86\u91cd\u6c2e\u5316\u5408\u7269\u4e0e\u4e9a\u80fa\uff0c\u9187\u6216\u6c28\u57fa\u7532\u9178\u916f\u7684\u4e0d\u5bf9\u79f0\u4e09\u7ec4\u5206\u4e32\u8054\u53cd\u5e94<span lang=\"EN-US\">(\u56fe<\/span><span lang=\"EN-US\">1B)<sup>[3]<\/sup><\/span>\u3002\u4eb2\u7535\u5b50\u4fa7\u7684\u4e0d\u5bf9\u79f0\u63a7\u5236\u4e0e\u4f20\u7edf\u65b9\u6cd5\u4e0d\u540c\uff0c\u5e76\u4e14\u53ef\u4ee5\u4f7f\u7528\u5176\u4ed6\u65b0\u7684\u4eb2\u6838\u8bd5\u5242\uff0c\u4f46\u4eb2\u7535\u8bd5\u5242\u76ee\u524d\u63a2\u8ba8\u7684\u8fd8\u5c40\u9650\u5728\u53ef\u4ee5\u5f62\u6210\u6c22\u952e\u7684\u7a33\u5b9a\u4e9a\u80fa\u7c7b\u5316\u5408\u7269\u3002\u6b64\u5916\uff0c\u672c\u65b9\u6cd5\u662f\u57fa\u4e8e<span lang=\"EN-US\">Asymmetric Counter\u2013Anion\u2013Directed Catalysis (ACDC)\u8fdb\u884c\u7684\u624b\u6027\u63a7\u5236\uff0c\u4e5f\u662f\u7b2c\u4e00\u6b21\u901a\u8fc7\u8fd9\u79cd\u7b56\u7565\u5b9e\u73b0\u4e86\u6c28\u57fa\u7532\u57fa\u5316<\/span><sup><span lang=\"EN-US\">[4]<\/span><\/sup>\u3002<\/p>\n<div id=\"attachment_63155\" class=\"wp-caption aligncenter\">\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-24828 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/03\/2019-03-01_12-59-39-680x332.png\" alt=\"\" width=\"680\" height=\"332\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/03\/2019-03-01_12-59-39-680x332.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/03\/2019-03-01_12-59-39-300x147.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/03\/2019-03-01_12-59-39-768x375.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/03\/2019-03-01_12-59-39-550x270.png 550w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/03\/2019-03-01_12-59-39.png 929w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/p>\n<p class=\"wp-caption-text\">\u56fe1.(A) \u5e38\u89c4\u7684\u4e0d\u5bf9\u79f0\u6c28\u57fa\u7532\u57fa\u5316 (B) \u624b\u6027\u78f7\u9178\u4e0e\u6c22\u952e\u4ecb\u5bfc\u4e0b\u7684\u4e9a\u80fa\u53c2\u4e0e\u7684\u624b\u6027\u8bf1\u5bfc<\/p>\n<\/div>\n<blockquote>\n<p class=\"a\"><b><span lang=\"EN-CA\">\u201cAsymmetric Counter\u2013Anion\u2013Directed Aminomethylation: Synthesis of Chiral \u03b2<\/span><\/b><b><span lang=\"EN-US\">\u2013Amino\u00a0<\/span><\/b><b><span lang=\"EN-CA\">Acids via Trapping of an Enol Intermediate\u201d<\/span><\/b><\/p>\n<p class=\"a\"><span lang=\"EN-CA\">Kang, Z.; Wang, Y.; Zhang, D.; Wu, R.; Xu, X.; Hu, W<\/span><span lang=\"EN-US\">. <i>J. Am. Chem. Soc.\u00a0<\/i><\/span><i><\/i><b><span lang=\"EN-US\">2019<\/span><\/b><span lang=\"EN-US\">, <i>141<\/i>, 1473.\u00a0<\/span><span lang=\"EN-CA\">DOI: <\/span><span lang=\"EN-US\"><span lang=\"EN-CA\"><a href=\"https:\/\/doi.org\/10.1021\/jacs.8b12832\">10.1021\/jacs.8b12832<\/a><\/span><\/span><\/p>\n<\/blockquote>\n<h4>\u8bba\u6587\u4f5c\u8005\u4ecb\u7ecd<\/h4>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-24829\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/03\/2019-03-01_18-24-36.png\" alt=\"\" width=\"142\" height=\"204\" \/><\/p>\n<p>\u7814\u7a76\u8005\uff1a<a href=\"\/\/www.gsbet888.com\/chemists\/2018\/03\/%e8%83%a1%e6%96%87%e6%b5%a9.html\"><strong>Wenhao Hu<\/strong><\/a>\uff08\u8bf7\u6233\u94fe\u63a5\uff09<\/p>\n<p>\u5c65\u5386\uff1a<br \/>\n1983-1987 B.S. Sichuan University<br \/>\n1987-1990 M.S. Chengdu Institute of Organic Chemistry (CIOC)<br \/>\n1995-1998 Ph.D. Hong Kong Polytechnic University (Prof. Albert S. C. Chan)<br \/>\n1998-2001 Posdoc, University of Arizona (Prof. Michael P. Doyle)<br \/>\n2002-2006 Medicinal Chemist (Genesoft), Process Chemist (Bristol\u2013Myers)<br \/>\n2006-2016 Professor, Department of Chemistry, East China Normal University<br \/>\n2016-\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0 Professor, School of Pharmaceutical Sciences, Sun Yat-Sen University<\/p>\n<p>\u7814\u7a76\u5185\u5bb9\uff1a\u901a\u8fc7\u6d3b\u6027\u4e2d\u95f4\u4f53\u6355\u6349\u8fdb\u884c\u591a\u7ec4\u5206\u53cd\u5e94<\/p>\n<h4 class=\"1\">\u8bba\u6587\u6982\u8981<\/h4>\n<p class=\"a\">\u80e1\u6587\u6d69\u6559\u6388\u7b49\u4eba\u3001\u901a\u8fc7ACDC\u7b56\u7565\uff0c\u6355\u6349\u4e9a\u80fa\u79bb\u5b50\u5b9e\u73b0\u4e0d\u5bf9\u79f0\u6c28\u57fa\u7532\u57fa\u5316<span lang=\"EN-US\">(\u56fe<\/span><span lang=\"EN-US\">2A)<\/span>\u3002\u9996\u5148\u4f5c\u8005\u4ece\u624b\u6027Br\u00f8nsteds\u9178\u5f00\u59cb\u8fdb\u884c\u7b5b\u9009\u3002\u7136\u800c\uff0c\u5373\u4f7f\u7b5b\u9009\u4e86\u591a\u79cd\u624b\u6027\u78f7\u9178\u50ac\u5316\u5242\uff0c\u4f9d\u7136\u6ca1\u6709\u53d1\u73b0\u5f88\u597d\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002\u5728\u8fd9\u91cc\uff0c\u80e1\u6559\u6388\u7b49\u4eba\u6539\u7528<span lang=\"EN-US\">Lambert\u7b49\u4eba\u57282016\u5e74\u62a5\u9053\u7684\u542b\u6709\u73af\u620a\u4e8c\u70ef\u57fa\u9aa8\u67b6\u7684Br\u00f8nsteds\u9178<\/span><span lang=\"EN-US\">(<b>5d<\/b>, <b>5e<\/b>)<sup>(5)<\/sup><\/span>\u3001\u7ec8\u4e8e\u5b9e\u73b0\u4e86\u6ee1\u610f\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002\u672c\u53cd\u5e94\u5e95\u7269\u9002\u7528\u8303\u56f4\u5e7f\uff0c\u5bf9\u4e8e<span lang=\"EN-US\">\u03b1<\/span><span lang=\"EN-US\">\u2013\u91cd\u6c2e\u916f\uff0c\u5bf9\u542b\u6709\u82b3\u9999\u73af\u53d6\u4ee3\u57fa<\/span><span lang=\"EN-US\">(<b>4b<\/b>~<b>4f<\/b>)\u82ef\u4e59\u70ef\u53d6\u4ee3\u57fa<\/span><span lang=\"EN-US\">(<b>4g<\/b>)\u7b49\u5e95\u7269\u90fd\u9002\u7528<\/span>\u3002\u9664\u9187\u548c\u82c4\u9187\u5916\uff0c\u8102\u65cf\u9187\uff08<strong>4h<span lang=\"EN-US\">~<\/span>4l<\/strong>\uff09\u548c\u5e26\u6742\u73af\u7684\u9187\uff08<strong>4m<\/strong>\uff09\u4e5f\u540c\u6837\u9002\u7528\u3002\u5bf9\u4e8e\u5e95\u7269\u80fa\u6765\u8bf4\uff0c\u82b3\u9999\u73af\u4e0a\u7684\u53d6\u4ee3\u57fa\u7684\u53d8\u5316<span lang=\"EN-US\">(<b>4n<\/b>~<b>4p<\/b>)<\/span>\u5e76\u6ca1\u6709\u5f71\u54cd\u53cd\u5e94\u7684\u8fdb\u884c<span lang=\"EN-US\">(\u56fe<\/span><span lang=\"EN-US\">2B)<\/span>\u3002\u6b64\u5916\uff0c<strong>4<\/strong>\u53ef\u4ee5\u8fdb\u4e00\u6b65\u884d\u751f\u4e3a\u03b1-\u7f9f\u57fa-\u03b2-\u6c28\u57fa\u9178\u6216\u03b1-\u7f9f\u57fa-\u03b2-\u5185\u9170\u80fa\u3002\u4f5c\u8005\u901a\u8fc7\u5b9e\u9a8c\u7ed3\u679c\u4e0eDFT\u7684\u8ba1\u7b97\u7ed3\u679c\u63a8\u6d4b\u51fa\u8be5\u53cd\u5e94\u7684\u53cd\u5e94\u673a\u7406\u5982\u56fe2C\u6240\u793a\u3002\u9996\u5148\uff0c<b><span lang=\"EN-US\">1<\/span><\/b>\u4e0e<span lang=\"EN-US\">Pd\u53cd\u5e94\u5f62\u6210\u5361\u5bbe\u4e2d\u95f4\u4f53<\/span><b>\u2160<\/b>\u3002<b>\u2160<\/b>\u88ab\u9187\u4eb2\u6838\u8fdb\u653b\uff0c\u7136\u540e\u53d1\u751fPd\u79bb\u53bb\u4e0e\u8d28\u5b50\u8f6c\u79fb\u5f62\u6210\u70ef\u9187<b>\u2161<\/b>\u3002\u53e6\u4e00\u65b9\u9762\u3001<b><span lang=\"EN-US\">3<\/span><\/b>\u5728<b><span lang=\"EN-US\">5d<\/span><\/b>\u5171\u5b58\u4e0b\u5f88\u5bb9\u6613\u7684\u53d1\u751f\u7532\u9187\u79bb\u53bb\u4ea7\u751f\u79bb\u5b50\u5bf9<b>\u2162<\/b>\u3002\u8be5<b>\u2162<\/b>\u7684\u4e9a\u80fa\u79bb\u5b50\u4e0e\u70ef\u9187<b>\u2161<\/b>\u8fdb\u884c<span lang=\"EN-US\">Mannich<\/span>\u578b\u53cd\u5e94\u6700\u7ec8\u751f\u6210\u4ea7\u7269<b><span lang=\"EN-US\">4<\/span><\/b>\u3002\u901a\u8fc7DFT\u63a8\u65ad\u8be5\u53cd\u5e94\u7684\u673a\u7406\u7684\u8be6\u7ec6\u5185\u5bb9\u8bf7\u53c2\u7167\u539f\u8bba\u6587\u3002<\/p>\n<div id=\"attachment_63174\" class=\"wp-caption aligncenter\">\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-24830 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/03\/2019-03-01_18-21-55-680x409.png\" alt=\"\" width=\"680\" height=\"409\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/03\/2019-03-01_18-21-55-680x409.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/03\/2019-03-01_18-21-55-300x181.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/03\/2019-03-01_18-21-55-768x462.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/03\/2019-03-01_18-21-55.png 939w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/p>\n<p class=\"wp-caption-text\">\u56fe2. (A) \u624b\u6027\u78f7\u9178\u8bd5\u5242\u63a2\u8ba8 (B) \u5e95\u7269\u9002\u7528\u8303\u56f4 (C) \u5047\u5b9a\u7684\u53cd\u5e94\u673a\u7406<\/p>\n<\/div>\n<p>&nbsp;<\/p>\n<p>\u7efc\u4e0a\u3001\u901a\u8fc7\u4f7f\u7528\u624b\u6027Br\u00f8nsteds\u9178<b><span lang=\"EN-US\">5d<\/span><\/b>\u5b9e\u73b0\u4e86\u9ad8\u5bf9\u6620\u9009\u62e9\u6027\u7684\u6c28\u57fa\u7532\u57fa\u5316\u3002\u5f88\u671f\u5f85\u4eca\u540e\u672c\u53cd\u5e94\u5728\u836f\u7269\u5c0f\u5206\u5b50\u5408\u6210\u4e0e\u5929\u7136\u4ea7\u7269\u5168\u5408\u6210\u4e0a\u7684\u5e94\u7528\u3002<\/p>\n<h4>\u53c2\u8003\u6587\u732e<\/h4>\n<ol>\n<li>Selected examples see: (a) Seayad, A.; Ahmed, M.; Klein, H.; Jackstell, R.; Gross, T.; Beller, M. <em>Science\u00a0<\/em><strong>2002<\/strong>, <em>297<\/em>, 1676. DOI: <a href=\"https:\/\/doi.org\/10.1126\/science.1074801\">1126\/science.1074801<\/a>(b) Remeur, C.; Kelly, C. B.; Patel, N. R.; Molander, G. A. <em>ACS Catal. <\/em><strong>2017<\/strong>, <em>7<\/em>, 6065. DOI: <a href=\"https:\/\/doi.org\/10.1021\/acscatal.7b01973\">10.1021\/acscatal.7b01973<\/a> \u307b\u307c\u540c\u6642\u671f\u306b\u4e0d\u6589\u53cd\u5fdc\u3067\u306f\u306a\u3044\u304c\u3001\u985e\u4f3c\u53cd\u5fdc\u304c\u5831\u544a\u3055\u308c\u305f(c) Zhang , Y.; Yu, B.; Gao, B.; Zhang, T.; Huang, H. <em>Org. Lett.\u00a0<\/em><strong>2019<\/strong>, <em>21<\/em>, 535. DOI:<a href=\"https:\/\/doi.org\/10.1021\/acs.orglett.8b03847\">10.1021\/acs.orglett.8b03847<\/a>(d) Fujii, S.; Konishi, T.; Matsumoto, Y.; Yamaoka, Y.; Takasu, K.; Yamada, K. <em>J. Org. Chem.\u00a0<\/em><strong>2014<\/strong>, <em>79<\/em>, 8128. DOI: <a href=\"https:\/\/doi.org\/10.1021\/jo501332j\">10.1021\/jo501332j<\/a><\/li>\n<li>(a) Ibrahem, I.; Casas, J.; Cordova, A. <em>Angew.<\/em>\u00a0<em>Chem., Int. Ed.\u00a0<\/em><strong>2004<\/strong>, <em>43<\/em>, 6528. DOI: <a href=\"https:\/\/doi.org\/10.1002\/anie.200460678\">10.1002\/anie.200460678<\/a>(b) Chi, Y.; Gellman, S. H. <em>J. Am. Chem. Soc.\u00a0<\/em><strong>2006<\/strong>, <em>128<\/em>, 6804. DOI: <a href=\"https:\/\/doi.org\/10.1021\/ja061731n\">10.1021\/ja061731n<\/a>(c) You, Y.; Zhang, L.; Cui, L.; Mi, X.; Luo, S. <em>Angew. Chem., Int. Ed. <\/em><strong>2017<\/strong>, <em>56<\/em>, 13814. DOI: <a href=\"https:\/\/doi.org\/10.1002\/anie.201707005\">10.1002\/anie.201707005<\/a><\/li>\n<li>Selected examples see (a) Hu, W. H.; Xu, X. F.; Zhou, J.; Liu, W. J.; Huang, H. X.; Hu, J.; Yang, L. P.; Gong, L. Z. <em>J.<\/em>\u00a0<em>Am. Chem. Soc.<\/em><strong>2008<\/strong>, <em>130<\/em>, 7782. DOI: <a href=\"https:\/\/doi.org\/10.1021\/ja801755z\">10.1021\/ja801755z<\/a> (b) Jiang, J.; Xu, H.-D.; Xi, J.-B.; Ren, B.-Y.; Lv, F.-P.; Guo, X.; Jiang, L.-Q.; Zhang, Z.-Y.: Hu, W. H. <em>J. Am. Chem. Soc.\u00a0<\/em><strong>2011<\/strong>, <em>133<\/em>, 8428. DOI: <a href=\"https:\/\/doi.org\/10.1021\/ja201589k\">10.1021\/ja201589k<\/a><\/li>\n<li>(a) Phipps, R.; Hamilton, G.; Toste, F. D. <em>Nat.<\/em>\u00a0<em>Chem.<\/em><strong>2012<\/strong>, <em>4<\/em>, 603. DOI: <a href=\"https:\/\/doi.org\/10.1038\/nchem.1405\">10.1038\/nchem.1405<\/a>(b) Mahlau, M.; List, B. <em>Angew. Chem., Int. Ed.\u00a0<\/em><strong>2013,<\/strong><em>52<\/em>, 518 DOI: <a href=\"https:\/\/doi.org\/10.1002\/anie.201205343\">10.1002\/anie.201205343<\/a>(c) Brak, K.; Jacobsen, E. N. <em>Angew. Chem., Int. Ed.\u00a0<\/em><strong>2013<\/strong>, <em>52<\/em>, 534. DOI: <a href=\"https:\/\/doi.org\/10.1002\/anie.201205449\">10.1002\/anie.201205449<\/a><\/li>\n<li>Gheewala, C. D.; Collins, B. E.; Lambert. <em>Science\u00a0<\/em><strong>2016<\/strong>, <em>351<\/em>, 961. DOI: <a href=\"https:\/\/doi.org\/10.1126\/science.aad0591\">1126\/science.aad0591<\/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":"\u6700\u8fd1\uff0c\u4e2d\u5c71\u5927\u5b66\u836f\u5b66\u9662\u80e1\u6587\u6d69\u6559\u6388\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86\u901a\u8fc7\u63a7\u5236\u4e9a\u80faCounter-Anion\u6765\u63a7\u5236\u624b\u6027\u7684\u80fa\u57fa\u7532\u57fa\u5316\u65b9\u6cd5\u3002 \u6c28\u57fa\u7532\u57fa\u5316\u4e0e\u5176\u624b\u6027\u63a7\u5236\u6cd5 \u5929\u7136\u4ea7\u7269\u4e0e\u533b\u836f\u5c0f\u5206\u5b50\u4e2d\u9891\u51fa\u7684\u300c\u6c28\u57fa\u7532\u57fa\u57fa\u56e2\u300d\u3001\u56e0\u6b64\u5f00\u53d1\u4e00\u79cd\u9ad8\u6548\u7684\u6c28\u57fa\u7532\u57fa\u5316\u65b9\u6cd5\u662f\u975e\u5e38\u6709\u4ef7\u503c\u7684\u3002\u8fc4\u4eca\u4e3a\u6b62\uff0c\u5df2\u7ecf\u62a5\u9053\u4e86\u5f88\u591a\u901a\u8fc7\u91d1\u5c5e\u50ac\u5316\u53cd\u5e94\u4e0e\u81ea\u7531\u57fa\u53cd\u5e94\u8fdb\u884c\u7684\u6c28\u57fa\u7532\u57fa\u5316\u5b9e\u4f8b[1]\u3002\u7136\u800c\uff0c\u50ac\u5316\u4e0d\u5bf9\u79f0\u6c28\u57fa\u7532\u57fa\u5316\u7684\u5b9e\u4f8b\u8fd8\u662f\u5f88\u6709\u9650\u3002\u5176\u4e2d\u7684\u4ee3\u8868\u6027\u5b9e\u4f8b\u6709\uff0c\u812f\u6c28\u9178\u50ac\u5316\u4e0b\u7684\u66fc\u5c3c\u5e0c\u578b\u916e\u548c\u4e9a\u80fa\u79bb\u5b50\u7684\u4e0d\u5bf9\u79f0\u6c28\u57fa\u7532\u57fa\u5316\uff08\u56fe1A\uff09[2a]\u3002\u7531\u916e\u548c\u812f\u6c28\u9178\u4ea7\u751f\u7684\u624b\u6027\u70ef\u80fa\uff08\u4eb2\u6838\u8bd5\u5242\uff09\u901a\u8fc7\u5bf9\u4f53\u7cfb\u4e2d\u751f\u6210\u7684\u4e9a\u80fa\u79bb\u5b50\uff08\u4eb2\u7535\u8bd5\u5242\uff09\u8fdb\u884c\u4eb2\u6838\u653b\u51fb\u6765\u4ea7\u751f\u624b\u6027\u4ea7\u7269\u3002\u6b64\u5916\uff0c\u5df2\u7ecf\u62a5\u9053\u4e86\u5728\u5176\u4ed6\u624b\u6027\u80fa\u50ac\u5316\u5242\u5b58\u5728\u4e0b\u4f7f\u7528\u919b[2b]\u548c1,3-\u4e8c\u916e\u4f5c\u4e3a\u4eb2\u6838\u8bd5\u5242[2c]\u7684\u7c7b\u4f3c\u7684\u4e0d\u5bf9\u79f0\u6c28\u57fa\u7532\u57fa\u5316\u53cd\u5e94\uff08\u56fe1B\uff09\u3002\u8fd9\u4e9b\u5b9e\u4f8b\u90fd\u662f\u5148\u5f62\u6210\u624b\u6027\u7684\u4eb2\u6838\u8bd5\u5242\u7136\u540e\u8fdb\u884c\u7684\u624b\u6027\u8bf1\u5bfc\uff0c\u56e0\u6b64\u5e95\u7269\u5c31\u5c40\u9650\u5728\u4e86\u53ef\u4ee5\u751f\u6210\u70ef\u80fa\u7684\u7fb0\u57fa\u5316\u5408\u7269\u4e0a\u3002 \u9488\u5bf9\u4e8e\u8fd9\u4e2a\u95ee\u9898\uff0c\u4e2d\u5c71\u5927\u5b66\u7684\u80e1\u6559\u6388\u8bfe\u9898\u7ec4\u7740\u773c\u4e8e\u624b\u6027\u78f7\u9178\u50ac\u5316\u5242\u3001\u5f00\u53d1\u51fa\u4e86\u91cd\u6c2e\u5316\u5408\u7269\u4e0e\u4e9a\u80fa\uff0c\u9187\u6216\u6c28\u57fa\u7532\u9178\u916f\u7684\u4e0d\u5bf9\u79f0\u4e09\u7ec4\u5206\u4e32\u8054\u53cd\u5e94(\u56fe1B)[3]\u3002\u4eb2\u7535\u5b50\u4fa7\u7684\u4e0d\u5bf9\u79f0\u63a7\u5236\u4e0e\u4f20\u7edf\u65b9\u6cd5\u4e0d\u540c\uff0c\u5e76\u4e14\u53ef\u4ee5\u4f7f\u7528\u5176\u4ed6\u65b0\u7684\u4eb2\u6838\u8bd5\u5242\uff0c\u4f46\u4eb2\u7535\u8bd5\u5242\u76ee\u524d\u63a2\u8ba8\u7684\u8fd8\u5c40\u9650\u5728\u53ef\u4ee5\u5f62\u6210\u6c22\u952e\u7684\u7a33\u5b9a\u4e9a\u80fa\u7c7b\u5316\u5408\u7269\u3002\u6b64\u5916\uff0c\u672c\u65b9\u6cd5\u662f\u57fa\u4e8eAsymmetric Counter\u2013Anion\u2013Directed Catalysis (ACDC)\u8fdb\u884c\u7684\u624b\u6027\u63a7\u5236\uff0c\u4e5f\u662f\u7b2c\u4e00\u6b21\u901a\u8fc7\u8fd9\u79cd\u7b56\u7565\u5b9e\u73b0\u4e86\u6c28\u57fa\u7532\u57fa\u5316[4]\u3002 \u56fe1.(A) \u5e38\u89c4\u7684\u4e0d\u5bf9\u79f0\u6c28\u57fa\u7532\u57fa\u5316 (B) \u624b\u6027\u78f7\u9178\u4e0e\u6c22\u952e\u4ecb\u5bfc\u4e0b\u7684\u4e9a\u80fa\u53c2\u4e0e\u7684\u624b\u6027\u8bf1\u5bfc \u201cAsymmetric Counter\u2013Anion\u2013Directed Aminomethylation: Synthesis of Chiral \u03b2\u2013Amino\u00a0Acids via Trapping of an Enol Intermediate\u201d Kang, Z.; Wang, Y.; Zhang, D.; Wu, R.; Xu, X.; Hu, W. J. Am. Chem. Soc.\u00a02019, 141, 1473.\u00a0DOI: 10.1021\/jacs.8b12832 \u8bba\u6587\u4f5c\u8005\u4ecb\u7ecd \u7814\u7a76\u8005\uff1aWenhao Hu\uff08\u8bf7\u6233\u94fe\u63a5\uff09 \u5c65\u5386\uff1a 1983-1987 B.S. Sichuan University 1987-1990 M.S. Chengdu Institute of Organic Chemistry (CIOC) 1995-1998 Ph.D. Hong Kong Polytechnic University (Prof. Albert S. C. Chan) 1998-2001 Posdoc, University of Arizona (Prof. Michael P. Doyle) 2002-2006 Medicinal Chemist (Genesoft), Process Chemist (Bristol\u2013Myers) 2006-2016 Professor, Department of Chemistry, East China Normal University 2016-\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0 Professor, School of Pharmaceutical Sciences, Sun Yat-Sen University \u7814\u7a76\u5185\u5bb9\uff1a\u901a\u8fc7\u6d3b\u6027\u4e2d\u95f4\u4f53\u6355\u6349\u8fdb\u884c\u591a\u7ec4\u5206\u53cd\u5e94 \u8bba\u6587\u6982\u8981 \u80e1\u6587\u6d69\u6559\u6388\u7b49\u4eba\u3001\u901a\u8fc7ACDC\u7b56\u7565\uff0c\u6355\u6349\u4e9a\u80fa\u79bb\u5b50\u5b9e\u73b0\u4e0d\u5bf9\u79f0\u6c28\u57fa\u7532\u57fa\u5316(\u56fe2A)\u3002\u9996\u5148\u4f5c\u8005\u4ece\u624b\u6027Br\u00f8nsteds\u9178\u5f00\u59cb\u8fdb\u884c\u7b5b\u9009\u3002\u7136\u800c\uff0c\u5373\u4f7f\u7b5b\u9009\u4e86\u591a\u79cd\u624b\u6027\u78f7\u9178\u50ac\u5316\u5242\uff0c\u4f9d\u7136\u6ca1\u6709\u53d1\u73b0\u5f88\u597d\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002\u5728\u8fd9\u91cc\uff0c\u80e1\u6559\u6388\u7b49\u4eba\u6539\u7528Lambert\u7b49\u4eba\u57282016\u5e74\u62a5\u9053\u7684\u542b\u6709\u73af\u620a\u4e8c\u70ef\u57fa\u9aa8\u67b6\u7684Br\u00f8nsteds\u9178(5d, 5e)(5)\u3001\u7ec8\u4e8e\u5b9e\u73b0\u4e86\u6ee1\u610f\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002\u672c\u53cd\u5e94\u5e95\u7269\u9002\u7528\u8303\u56f4\u5e7f\uff0c\u5bf9\u4e8e\u03b1\u2013\u91cd\u6c2e\u916f\uff0c\u5bf9\u542b\u6709\u82b3\u9999\u73af\u53d6\u4ee3\u57fa(4b~4f)\u82ef\u4e59\u70ef\u53d6\u4ee3\u57fa(4g)\u7b49\u5e95\u7269\u90fd\u9002\u7528\u3002\u9664\u9187\u548c\u82c4\u9187\u5916\uff0c\u8102\u65cf\u9187\uff084h~4l\uff09\u548c\u5e26\u6742\u73af\u7684\u9187\uff084m\uff09\u4e5f\u540c\u6837\u9002\u7528\u3002\u5bf9\u4e8e\u5e95\u7269\u80fa\u6765\u8bf4\uff0c\u82b3\u9999\u73af\u4e0a\u7684\u53d6\u4ee3\u57fa\u7684\u53d8\u5316(4n~4p)\u5e76\u6ca1\u6709\u5f71\u54cd\u53cd\u5e94\u7684\u8fdb\u884c(\u56fe2B)\u3002\u6b64\u5916\uff0c4\u53ef\u4ee5\u8fdb\u4e00\u6b65\u884d\u751f\u4e3a\u03b1-\u7f9f\u57fa-\u03b2-\u6c28\u57fa\u9178\u6216\u03b1-\u7f9f\u57fa-\u03b2-\u5185\u9170\u80fa\u3002\u4f5c\u8005\u901a\u8fc7\u5b9e\u9a8c\u7ed3\u679c\u4e0eDFT\u7684\u8ba1\u7b97\u7ed3\u679c\u63a8\u6d4b\u51fa\u8be5\u53cd\u5e94\u7684\u53cd\u5e94\u673a\u7406\u5982\u56fe2C\u6240\u793a\u3002\u9996\u5148\uff0c1\u4e0ePd\u53cd\u5e94\u5f62\u6210\u5361\u5bbe\u4e2d\u95f4\u4f53\u2160\u3002\u2160\u88ab\u9187\u4eb2\u6838\u8fdb\u653b\uff0c\u7136\u540e\u53d1\u751fPd\u79bb\u53bb\u4e0e\u8d28\u5b50\u8f6c\u79fb\u5f62\u6210\u70ef\u9187\u2161\u3002\u53e6\u4e00\u65b9\u9762\u30013\u57285d\u5171\u5b58\u4e0b\u5f88\u5bb9\u6613\u7684\u53d1\u751f\u7532\u9187\u79bb\u53bb\u4ea7\u751f\u79bb\u5b50\u5bf9\u2162\u3002\u8be5\u2162\u7684\u4e9a\u80fa\u79bb\u5b50\u4e0e\u70ef\u9187\u2161\u8fdb\u884cMannich\u578b\u53cd\u5e94\u6700\u7ec8\u751f\u6210\u4ea7\u72694\u3002\u901a\u8fc7DFT\u63a8\u65ad\u8be5\u53cd\u5e94\u7684\u673a\u7406\u7684\u8be6\u7ec6\u5185\u5bb9\u8bf7\u53c2\u7167\u539f\u8bba\u6587\u3002 \u56fe2. 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