{"id":32501,"date":"2020-06-09T08:04:26","date_gmt":"2020-06-09T00:04:26","guid":{"rendered":"\/\/www.gsbet888.com\/?p=32501"},"modified":"2020-06-09T08:04:26","modified_gmt":"2020-06-09T00:04:26","slug":"pdii%e5%82%ac%e5%8c%96%e5%bc%82%e4%b8%81%e7%a1%ab%e4%bb%a3%e9%85%b0%e8%83%ba%e7%9a%84%e4%b8%8d%e5%af%b9%e7%a7%b0%ce%b2-csp3-h%e5%ae%98%e8%83%bd%e5%9b%a2%e5%8c%96%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\/2020\/06\/pdii%e5%82%ac%e5%8c%96%e5%bc%82%e4%b8%81%e7%a1%ab%e4%bb%a3%e9%85%b0%e8%83%ba%e7%9a%84%e4%b8%8d%e5%af%b9%e7%a7%b0%ce%b2-csp3-h%e5%ae%98%e8%83%bd%e5%9b%a2%e5%8c%96%e5%8f%8d%e5%ba%94.html","title":{"rendered":"Pd(II)\u50ac\u5316\u5f02\u4e01\u786b\u4ee3\u9170\u80fa\u7684\u4e0d\u5bf9\u79f0\u03b2-C(sp3)-H\u5b98\u80fd\u56e2\u5316\u53cd\u5e94"},"content":{"rendered":"<p>\u8102\u80aa\u65cfC(sp<sup>3<\/sup>)-H\u5b98\u80fd\u56e2\u5316\u4e00\u76f4\u5b58\u5728C\u2012H\u952e\u80fd\u529b\u9ad8\u3001\u9178\u5ea6\u4f4e\u3001\u4ee5\u53ca\u5206\u5b50\u8f68\u9053\u4e0d\u6d3b\u6cfc\u7b49\u95ee\u9898\uff0c\u56e0\u6b64\u5b9e\u73b0\u8102\u80aa\u65cfC(sp<sup>3<\/sup>)-H\u5b98\u80fd\u56e2\u5316\u4e00\u76f4\u662f\u5316\u5b66\u5bb6\u4eec\u5173\u6ce8\u7684\u91cd\u70b9\u3002\u968f\u7740\u65f6\u4ee3\u7684\u53d1\u5c55\uff0c\u5e94\u7528\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u786b\u9170\u80fa\u3001\u53d4\u4e01\u57fa\u786b\u4ee3\u9170\u80fa\u53d6\u4ee3\u76841,2,3,4-\u56db\u6c22\u55b9\u5549\u4ee5\u53ca\u4e8c\u6076\u5511\u916e\u53d1\u751f\u5bf9\u6620\u9009\u62e9\u6027\u80fa\u03b1-C(sp<sup>3<\/sup>)\u2012H\u82b3\u57fa\u5316\u53cd\u5e94\u7684\u7b56\u7565\u5f97\u5230\u4e86\u4e00\u5b9a\u7684\u53d1\u5c55<sup>[1]<\/sup>\u3002\u4e01\u786b\u4ee3\u9170\u80fa\u7684\u53bb\u5bf9\u79f0\u5316\u53cd\u5e94\u53ef\u4ee5\u6709\u6548\u7684\u5408\u6210\u5177\u6709\u91cd\u8981\u4f5c\u7528\u7684\u624b\u6027\u03b2-\u82b3\u57fa\u5f02\u4e01\u9170\u80fa\u53ca\u5176\u884d\u751f\u7269\uff0c\u4f46\u5230\u76ee\u524d\u4e3a\u6b62\uff0c\u8fd8\u6ca1\u6709\u76f8\u5173\u62a5\u9053(Scheme 1a)\u3002\u4e3a\u4e86\u5b9e\u73b0\u4e01\u786b\u4ee3\u9170\u80fa\u7684C(sp<sup>3<\/sup>)\u2012H\u82b3\u57fa\u5316\u8fc7\u7a0b\uff0c\u4e2d\u56fd\u79d1\u5b66\u6280\u672f\u5927\u5b66\u9f9a\u6d41\u67f1\u56e2\u961f\u8fdb\u884c\u4e86\u7cfb\u7edf\u7684\u6587\u732e\u8c03\u7814\u5e76\u53d1\u73b0\u786b\u9170\u80fa\u4e2dN-\u53d6\u4ee3\u57fa\u7684\u4f4d\u963b\u5927\u5c0f\u53ef\u4ee5\u8c03\u63a7C(sp<sup>3<\/sup>)-H\u7684\u6d3b\u5316\u4f4d\u70b9<sup>[2]<\/sup>(Scheme 1b)\u3002\u4e3a\u4e86\u8bc1\u5b9e\u8fd9\u4e2a\u731c\u60f3\uff0c\u5317\u4eac\u5927\u5b66<a href=\"http:\/\/scbb.pkusz.edu.cn\/2015\/theoretical_0714\/43.html\">\u5f20\u6b23\u8c6a\u8bfe\u9898\u7ec4<\/a>\u901a\u8fc7\u5bc6\u5ea6\u6cdb\u51fd\u7406\u8bba\uff08DFT\uff09\u8ba1\u7b97\u663e\u793aN\u53d6\u4ee3\u57fa\u53d8\u5927\uff0cC\u2013H\u952e\u65ad\u88c2\u7684\u4f4d\u70b9\u8d8a\u63a5\u8fd1\u786b\u4ee3\u9170\u80fa(Scheme 1c)\u3002\u5728\u4e0a\u8ff0\u80cc\u666f\u7814\u7a76\u7684\u57fa\u7840\u4e0a\uff0c\u4e2d\u56fd\u79d1\u5b66\u6280\u672f\u5927\u5b66<a href=\"http:\/\/www.hfnl.ustc.edu.cn\/detail?id=11339\">\u9f9a\u6d41\u67f1\u56e2\u961f<\/a>\u6210\u529f\u62a5\u9053\u4e86\u9996\u4f8bPd(II)\u50ac\u5316N,N-\u4e8c\u5f02\u4e19\u57fa\u80fa\u57fa\u5f02\u4e01\u786b\u4ee3\u9170\u80fa\u7684\u4e0d\u5bf9\u79f0\u03b2-C(sp<sup>3<\/sup>)-H\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\uff0c\u80fd\u4ee5\u4f18\u79c0\u7684\u6536\u7387\u548c\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230\u4e00\u7cfb\u5217\u624b\u6027\u03b2-\u82b3\u57fa\u5f02\u4e01\u9170\u80fa\u3002\u76f8\u5173\u6210\u679c\u53d1\u8868\u4e8e<\/p>\n<blockquote><p>\u201cHybrid Palladium Catalyst Assembled from Chiral Phosphoric Acid and Thioamide for Enantioselective \u03b2-C(sp<sup>3<\/sup>)\u2012H Arylation\u201d<\/p>\n<p>Jiang, H.-J.; Zhong, X.-M.; Liu, Z.-Y.; Geng, R.-L.; Li, Y.-Y.; Wu, Y.-D.; Zhang, X.* Gong, L.-Z.* <em>Angew. Chem. Int. Ed. <\/em><strong>2020<\/strong>, Accepted Article. DOI: <a href=\"https:\/\/onlinelibrary.wiley.com\/doi\/abs\/10.1002\/anie.202004485\">10.1002\/anie.202004485<\/a><\/p><\/blockquote>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/1-52.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-32502 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/1-52.jpg\" alt=\"\" width=\"472\" height=\"580\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/1-52.jpg 472w, https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/1-52-244x300.jpg 244w\" sizes=\"(max-width: 472px) 100vw, 472px\" \/><\/a><\/p>\n<p style=\"text-align: center;\">Scheme 1. \u7814\u7a76\u80cc\u666f<\/p>\n<h4><strong>\u8bba\u6587\u4f5c\u8005\u4ecb\u7ecd<\/strong><\/h4>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/2-50.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-32503 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/2-50.jpg\" alt=\"\" width=\"447\" height=\"344\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/2-50.jpg 447w, https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/2-50-300x231.jpg 300w\" sizes=\"(max-width: 447px) 100vw, 447px\" \/><\/a><\/p>\n<p style=\"text-align: center;\">\u9f9a\u6d41\u67f1\u6559\u6388<\/p>\n<p><span style=\"color: #0000ff;\"><strong>\u7814\u7a76\u7ecf\u5386<\/strong><\/span><\/p>\n<ul>\n<li>1989.09-1993.07\uff0c\u6cb3\u5357\u5e08\u8303\u5927\u5b66\u5316\u5b66\u7cfb\uff0c\u5316\u5b66\u6559\u80b2\u4e13\u4e1a\uff0c\u7406\u5b66\u5b66\u58eb\uff1b<\/li>\n<li>1993.09-1996.07\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u6210\u90fd\u6709\u673a\u5316\u5b66\u7814\u7a76\u6240\uff0c\u6709\u673a\u5408\u6210\uff0c\u7406\u5b66\u7855\u58eb\uff1b<\/li>\n<li>1996.09-1998.06\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u5316\u5b66\u7814\u7a76\u6240\uff0c\u6709\u673a\u5408\u6210\uff0c\u535a\u58eb\u751f\uff1b<\/li>\n<li>1998.06-2000.06\uff0c\u7f8e\u56fd\u5f17\u5409\u5c3c\u4e9a\u5927\u5b66 (University of Virginia)\u5316\u5b66\u7cfb\uff0c\u8bbf\u95ee\u5b66\u8005\uff08\u8054\u5408\u57f9\u517b\u535a\u58eb\u751f\uff09\uff1b<\/li>\n<li>2000.07\uff0c\u83b7\u4e2d\u56fd\u79d1\u5b66\u9662\u5316\u5b66\u7814\u7a76\u6240\u7406\u5b66\u535a\u58eb\u5b66\u4f4d\u3002<\/li>\n<\/ul>\n<p><strong><span style=\"color: #0000ff;\">\u4e3b\u8981\u7ecf\u5386<\/span><\/strong><\/p>\n<ul>\n<li>2000.12-2001.11\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u6210\u90fd\u6709\u673a\u5316\u5b66\u7814\u7a76\u6240\uff0c\u52a9\u7406\u7814\u7a76\u5458\uff1b<\/li>\n<li>2000.12-2001.11\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u6210\u90fd\u6709\u673a\u5316\u5b66\u7814\u7a76\u6240\uff0c\u526f\u7814\u7a76\u5458<\/li>\n<li>2001.12-2005.12\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u6210\u90fd\u6709\u673a\u5316\u5b66\u7814\u7a76\u6240\uff0c\u7814\u7a76\u5458\uff0c\u535a\u58eb\u751f\u5bfc\u5e08\uff0c\u5148\u540e\u4efb\u4e0d\u5bf9\u79f0\u5408\u6210\u548c\u624b\u6027\u6280\u672f\u56db\u5ddd\u7701\u91cd\u70b9\u5b9e\u9a8c\u5ba4\u5e38\u52a1\u526f\u4e3b\u4efb\uff0c\u4e3b\u4efb\uff1b<\/li>\n<li>2003.10-2004.09\uff0c\u5fb7\u56fd\u6155\u5c3c\u9ed1\u5927\u5b66(Ludwig-Maximilians-Universit\u00e4t M\u00fcnchen) \u6709\u673a\u5316\u5b66\u7814\u7a76\u6240, \u6d2a\u5821\u5b66\u8005\uff0c\u8bbf\u95ee\u6559\u6388\uff1b<\/li>\n<li>2006.01-\u81f3\u4eca\uff0c\u4e2d\u56fd\u79d1\u5b66\u6280\u672f\u5927\u5b66\u5316\u5b66\u7cfb\uff0c\u5408\u80a5\u5fae\u5c3a\u5ea6\u7269\u8d28\u79d1\u5b66\u56fd\u5bb6\u7814\u7a76\u4e2d\u5fc3\uff0c\u6559\u6388\uff1b<\/li>\n<li>2011.01-\u81f3\u4eca\uff0c\u5408\u80a5\u5fae\u5c3a\u5ea6\u7269\u8d28\u79d1\u5b66\u56fd\u5bb6\u7814\u7a76\u4e2d\u5fc3\u4f4e\u7ef4\u7269\u7406\u4e0e\u5316\u5b66\u7814\u7a76\u90e8\u4e3b\u4efb\u3002<\/li>\n<\/ul>\n<p><strong><span style=\"color: #0000ff;\">\u7814\u7a76\u9886\u57df<\/span><\/strong><\/p>\n<ol>\n<li>\u6709\u673a\u5c0f\u5206\u5b50\u548c\u91d1\u5c5e\u201c\u534f\u540c\u201d\u6216\u201c\u63a5\u529b\u201d\u50ac\u5316\u7684\u53cd\u5e94\uff0c\u53d1\u5c55\u6784\u5efa\u590d\u6742\u7ed3\u6784\u624b\u6027\u5206\u5b50\u7684\u6b65\u9aa4\u7ecf\u6d4e\u6027\u53cd\u5e94\uff0c\u7814\u7a76\u5f71\u54cd\u534f\u540c\u548c\u63a5\u529b\u50ac\u5316\u7684\u89c4\u5f8b<\/li>\n<li>\u53d1\u5c55\u4e32\u8054\u53cd\u5e94\u3001\u73af\u52a0\u6210\u53cd\u5e94\u4ee5\u53ca\u4e0d\u5bf9\u79f0\u591a\u7ec4\u5206\u53cd\u5e94\u7b49\uff0c\u63a2\u7d22\u5feb\u901f\u6784\u5efa\u7ed3\u6784\u591a\u6837\u6027\u7684\u624b\u6027\u751f\u7406\u6d3b\u6027\u5206\u5b50\u7684\u5408\u6210\u65b9\u6cd5<\/li>\n<li>\u60f0\u6027\u78b3\u6c22\u952e\u7684\u4e0d\u5bf9\u79f0\u5b98\u80fd\u56e2\u5316<\/li>\n<li>\u50ac\u5316\u4e0d\u5bf9\u79f0\u5408\u6210\u590d\u6742\u5929\u7136\u751f\u7269\u78b1\u548c\u751f\u7406\u6d3b\u6027\u5206\u5b50<\/li>\n<\/ol>\n<h4><strong>\u8bba\u6587\u6982\u8981<\/strong><\/h4>\n<p>\u4ee5N,N-\u4e8c\u5f02\u4e19\u57fa\u80fa\u57fa\u5f02\u4e01\u786b\u4ee3\u9170\u80fa<strong>2a<\/strong>\u548c\u82ef\u787c\u9178\u4e3a\u6a21\u677f\u5e95\u7269\uff0c\u4f5c\u8005\u5bf9\u5404\u79cd\u53cd\u5e94\u6761\u4ef6\u8fdb\u884c\u53cd\u590d\u7b5b\u9009\uff0c\u786e\u5b9a\u6700\u4f73\u6761\u4ef6\u4e3a(Table 1)\uff1aN<sub>2<\/sub>\u4fdd\u62a4\u6761\u4ef6\u4e0b\uff0c5 mol\uff05Pd<sub>2<\/sub>(dba)<sub>3<\/sub>\u548c12 mol\uff05<strong>CPA1<\/strong>\u4e3a\u50ac\u5316\u5242\uff0c2 equiv 1,4-BQ\u4e3a\u6c27\u5316\u5242\uff0c 3 \u00c5\u5206\u5b50\u7b5b\u4e3a\u6dfb\u52a0\u7269\uff0c<em><sup>t<\/sup><\/em>AmylOH\u4e3a\u6eb6\u5242\uff0c\u572860 <sup>o<\/sup>C\u6761\u4ef6\u4e0b\u53cd\u5e9412 h\uff0c\u80fd\u4ee591%\u7684\u6536\u7387\u548c97%\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230\u76f8\u5e94\u4ea7\u7269<strong>3a<\/strong>\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/3-39.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-32504 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/3-39.jpg\" alt=\"\" width=\"569\" height=\"599\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/3-39.jpg 569w, https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/3-39-285x300.jpg 285w\" sizes=\"(max-width: 569px) 100vw, 569px\" \/><\/a><\/p>\n<p style=\"text-align: center;\">Table 1. \u6761\u4ef6\u7b5b\u9009<\/p>\n<p>\u5728\u6700\u4f18\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u5bf9\u82b3\u57fa\u787c\u9178\u7684\u5e95\u7269\u8303\u56f4\u8fdb\u884c\u4e86\u8003\u5bdf\u3002\u5404\u79cd\u5438\u7535\u5b50\u6216\u7ed9\u7535\u5b50\u53d6\u4ee3\u7684\u82ef\u787c\u9178\u5747\u80fd\u8f83\u597d\u7684\u9002\u5e94\u53cd\u5e94\u6761\u4ef6\uff0c\u80fd\u4ee5\u826f\u597d\u81f3\u4f18\u79c0\u7684\u6536\u7387\u53ca\u4f18\u79c0\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230\u76f8\u5e94\u4ea7\u7269\uff0c\u4f46\u7532\u57fa\u787c\u9178\u53ea\u80fd\u4ee518%\u7684\u6536\u7387\u548c56%\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230\u76f8\u5e94\u4ea7\u7269\u3002\u7d27\u63a5\u7740\uff0c\u4f5c\u8005\u5bf9\u5f02\u4e01\u786b\u4ee3\u9170\u80fa\u8fdb\u884c\u4e86\u52a8\u529b\u5b66\u62c6\u5206\u8fc7\u7a0b\u3002\u901a\u8fc7\u7b80\u5355\u7684\u6761\u4ef6\u4f18\u5316\u786e\u5b9a<strong>CPA6<\/strong>\u4e3a\u6700\u4f18\u50ac\u5316\u5242\u3002\u5728\u8be5\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u5404\u79cd\u53d6\u4ee3\u7684\u5f02\u4e01\u786b\u4ee3\u9170\u80fa\u90fd\u80fd\u4ee5\u4e2d\u7b49\u7684\u6536\u7387\u548c\u826f\u597d\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230\u76f8\u5e94\u7684\u4e8c\u82b3\u57fa\u4ea7\u7269\uff0c\u540c\u65f6\uff0c\u53ef\u4ee5\u56de\u6536\u91cd\u8981\u7684\u624b\u6027\u5f02\u4e01\u786b\u4ee3\u9170\u80fa\u5316\u5408\u7269\u3002<\/p>\n<p>\u4e3a\u4e86\u8bc1\u660e\u53cd\u5e94\u7684\u5e94\u7528\u6f5c\u529b\uff0c\u4f5c\u8005\u8fdb\u884c\u4e86\u4e00\u7cfb\u5217\u884d\u751f\u53cd\u5e94(Scheme 2)\u3002\u5728\u6700\u4f18\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c<strong>2a<\/strong>\u53ef\u4e0e4-\u6c2f\u82ef\u787c\u9178\u53d1\u751f\u6c27\u5316C\u2012H\u5076\u8054\u53cd\u5e94\uff0c\u80fd\u4ee592\uff05\u7684\u6536\u7387\u548c95\uff05\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230(<em>S<\/em>)-<strong>3f<\/strong>\u3002(<em>S<\/em>)-<strong>3f<\/strong>\u901a\u8fc7\u7b80\u5355\u7684\u5316\u5b66\u4fee\u9970\u5373\u53efS1P\u62ee\u6297\u5242\u3002\u540c\u65f6\uff0c\u4f5c\u8005\u901a\u8fc7MS\u5206\u6790\u548cDFT\u8ba1\u7b97\u5206\u6790\u8bc1\u5b9e\u4e86\u5927\u4f4d\u963b\u53d6\u4ee3\u7684\u624b\u6027\u78f7\u9178\u662f\u53cd\u5e94\u4ea7\u7269\u7684\u9ad8\u5bf9\u6620\u9009\u62e9\u6027\u7684\u5fc5\u8981\u6761\u4ef6\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/4-31.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-32505 \" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/4-31.jpg\" alt=\"\" width=\"694\" height=\"407\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/4-31.jpg 754w, https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/4-31-300x176.jpg 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/4-31-680x399.jpg 680w\" sizes=\"(max-width: 694px) 100vw, 694px\" \/><\/a><\/p>\n<p style=\"text-align: center;\">Scheme 2. \u884d\u751f\u53cd\u5e94<\/p>\n<h4><strong>\u8bba\u6587\u603b\u7ed3\u8bc4\u4ef7<\/strong><\/h4>\n<p>\u4e2d\u56fd\u79d1\u5b66\u6280\u672f\u5927\u5b66<a href=\"http:\/\/www.hfnl.ustc.edu.cn\/detail?id=11339\">\u9f9a\u6d41\u67f1\u56e2\u961f<\/a>\u6210\u529f\u62a5\u9053\u4e86\u9996\u4f8bPd(II)\u50ac\u5316N,N-\u4e8c\u5f02\u4e19\u57fa\u80fa\u57fa\u5f02\u4e01\u786b\u4ee3\u9170\u80fa\u7684\u4e0d\u5bf9\u79f0\u03b2-C(sp<sup>3<\/sup>)-H\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\uff0c\u80fd\u4ee5\u4f18\u79c0\u7684\u6536\u7387\u548c\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230\u4e00\u7cfb\u5217\u624b\u6027\u03b2-\u82b3\u57fa\u5f02\u4e01\u9170\u80fa\u3002\u5bc6\u5ea6\u6cdb\u51fd\u7406\u8bba\uff08DFT\uff09\u8ba1\u7b97\u663e\u793aN\u53d6\u4ee3\u57fa\u53d8\u5927\uff0cC\u2013H\u952e\u65ad\u88c2\u7684\u4f4d\u70b9\u8d8a\u63a5\u8fd1\u786b\u4ee3\u9170\u80fa\u3002<\/p>\n<h4><strong>\u53c2\u8003\u6587\u732e<\/strong><\/h4>\n<ul>\n<li>[1] (a) Jain, P.; Verma, P.; Xia, G.; Yu, J.-Q. <em> Chem<\/em>. <strong>2017<\/strong>, <em>9<\/em>, 140-144; DOI: <a href=\"https:\/\/www.nature.com\/articles\/nchem.2619\">10.1038\/nchem.2619<\/a> (b) Jiang, H.-J.; Zhong, X.-M.; Yu, J.; Zhang, Y.; Zhang, X.; Wu, Y.-D.; Gong, L.-Z. <em>Angew. Chem. Int. Ed.<\/em> <strong>2019<\/strong>, <em>58<\/em>, 1803-1807; DOI: <a href=\"https:\/\/onlinelibrary.wiley.com\/doi\/abs\/10.1002\/anie.201812426\">10.1002\/anie.201812426<\/a><\/li>\n<li>[2] Gre\u00dfies, S.; Klauck, F. J. R.; Kim, J. H.; Daniliuc, C. G.; Glorius, F. <em> Chem. Int. Ed.<\/em> <strong>2018<\/strong>, <em>57<\/em>, 9950-9954. DOI: <a href=\"https:\/\/onlinelibrary.wiley.com\/doi\/abs\/10.1002\/anie.201805680\">10.1002\/anie.201805680<\/a><\/li>\n<\/ul>\n<p>\u672c\u6587\u7248\u6743\u5c5e\u4e8e<strong>\u00a0<a href=\"\/\/www.gsbet888.com\/\">Chem-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":"\u8102\u80aa\u65cfC(sp3)-H\u5b98\u80fd\u56e2\u5316\u4e00\u76f4\u5b58\u5728C\u2012H\u952e\u80fd\u529b\u9ad8\u3001\u9178\u5ea6\u4f4e\u3001\u4ee5\u53ca\u5206\u5b50\u8f68\u9053\u4e0d\u6d3b\u6cfc\u7b49\u95ee\u9898\uff0c\u56e0\u6b64\u5b9e\u73b0\u8102\u80aa\u65cfC(sp3)-H\u5b98\u80fd\u56e2\u5316\u4e00\u76f4\u662f\u5316\u5b66\u5bb6\u4eec\u5173\u6ce8\u7684\u91cd\u70b9\u3002\u968f\u7740\u65f6\u4ee3\u7684\u53d1\u5c55\uff0c\u5e94\u7528\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u786b\u9170\u80fa\u3001\u53d4\u4e01\u57fa\u786b\u4ee3\u9170\u80fa\u53d6\u4ee3\u76841,2,3,4-\u56db\u6c22\u55b9\u5549\u4ee5\u53ca\u4e8c\u6076\u5511\u916e\u53d1\u751f\u5bf9\u6620\u9009\u62e9\u6027\u80fa\u03b1-C(sp3)\u2012H\u82b3\u57fa\u5316\u53cd\u5e94\u7684\u7b56\u7565\u5f97\u5230\u4e86\u4e00\u5b9a\u7684\u53d1\u5c55[1]\u3002\u4e01\u786b\u4ee3\u9170\u80fa\u7684\u53bb\u5bf9\u79f0\u5316\u53cd\u5e94\u53ef\u4ee5\u6709\u6548\u7684\u5408\u6210\u5177\u6709\u91cd\u8981\u4f5c\u7528\u7684\u624b\u6027\u03b2-\u82b3\u57fa\u5f02\u4e01\u9170\u80fa\u53ca\u5176\u884d\u751f\u7269\uff0c\u4f46\u5230\u76ee\u524d\u4e3a\u6b62\uff0c\u8fd8\u6ca1\u6709\u76f8\u5173\u62a5\u9053(Scheme 1a)\u3002\u4e3a\u4e86\u5b9e\u73b0\u4e01\u786b\u4ee3\u9170\u80fa\u7684C(sp3)\u2012H\u82b3\u57fa\u5316\u8fc7\u7a0b\uff0c\u4e2d\u56fd\u79d1\u5b66\u6280\u672f\u5927\u5b66\u9f9a\u6d41\u67f1\u56e2\u961f\u8fdb\u884c\u4e86\u7cfb\u7edf\u7684\u6587\u732e\u8c03\u7814\u5e76\u53d1\u73b0\u786b\u9170\u80fa\u4e2dN-\u53d6\u4ee3\u57fa\u7684\u4f4d\u963b\u5927\u5c0f\u53ef\u4ee5\u8c03\u63a7C(sp3)-H\u7684\u6d3b\u5316\u4f4d\u70b9[2](Scheme 1b)\u3002\u4e3a\u4e86\u8bc1\u5b9e\u8fd9\u4e2a\u731c\u60f3\uff0c\u5317\u4eac\u5927\u5b66\u5f20\u6b23\u8c6a\u8bfe\u9898\u7ec4\u901a\u8fc7\u5bc6\u5ea6\u6cdb\u51fd\u7406\u8bba\uff08DFT\uff09\u8ba1\u7b97\u663e\u793aN\u53d6\u4ee3\u57fa\u53d8\u5927\uff0cC\u2013H\u952e\u65ad\u88c2\u7684\u4f4d\u70b9\u8d8a\u63a5\u8fd1\u786b\u4ee3\u9170\u80fa(Scheme 1c)\u3002\u5728\u4e0a\u8ff0\u80cc\u666f\u7814\u7a76\u7684\u57fa\u7840\u4e0a\uff0c\u4e2d\u56fd\u79d1\u5b66\u6280\u672f\u5927\u5b66\u9f9a\u6d41\u67f1\u56e2\u961f\u6210\u529f\u62a5\u9053\u4e86\u9996\u4f8bPd(II)\u50ac\u5316N,N-\u4e8c\u5f02\u4e19\u57fa\u80fa\u57fa\u5f02\u4e01\u786b\u4ee3\u9170\u80fa\u7684\u4e0d\u5bf9\u79f0\u03b2-C(sp3)-H\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\uff0c\u80fd\u4ee5\u4f18\u79c0\u7684\u6536\u7387\u548c\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230\u4e00\u7cfb\u5217\u624b\u6027\u03b2-\u82b3\u57fa\u5f02\u4e01\u9170\u80fa\u3002\u76f8\u5173\u6210\u679c\u53d1\u8868\u4e8e \u201cHybrid Palladium Catalyst Assembled from Chiral Phosphoric Acid and Thioamide for Enantioselective \u03b2-C(sp3)\u2012H Arylation\u201d Jiang, H.-J.; Zhong, X.-M.; Liu, Z.-Y.; Geng, R.-L.; Li, Y.-Y.; Wu, Y.-D.; Zhang, X.* Gong, L.-Z.* Angew. Chem. Int. Ed. 2020, Accepted Article. DOI: 10.1002\/anie.202004485 Scheme 1. \u7814\u7a76\u80cc\u666f \u8bba\u6587\u4f5c\u8005\u4ecb\u7ecd \u9f9a\u6d41\u67f1\u6559\u6388 \u7814\u7a76\u7ecf\u5386 1989.09-1993.07\uff0c\u6cb3\u5357\u5e08\u8303\u5927\u5b66\u5316\u5b66\u7cfb\uff0c\u5316\u5b66\u6559\u80b2\u4e13\u4e1a\uff0c\u7406\u5b66\u5b66\u58eb\uff1b 1993.09-1996.07\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u6210\u90fd\u6709\u673a\u5316\u5b66\u7814\u7a76\u6240\uff0c\u6709\u673a\u5408\u6210\uff0c\u7406\u5b66\u7855\u58eb\uff1b 1996.09-1998.06\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u5316\u5b66\u7814\u7a76\u6240\uff0c\u6709\u673a\u5408\u6210\uff0c\u535a\u58eb\u751f\uff1b 1998.06-2000.06\uff0c\u7f8e\u56fd\u5f17\u5409\u5c3c\u4e9a\u5927\u5b66 (University of Virginia)\u5316\u5b66\u7cfb\uff0c\u8bbf\u95ee\u5b66\u8005\uff08\u8054\u5408\u57f9\u517b\u535a\u58eb\u751f\uff09\uff1b 2000.07\uff0c\u83b7\u4e2d\u56fd\u79d1\u5b66\u9662\u5316\u5b66\u7814\u7a76\u6240\u7406\u5b66\u535a\u58eb\u5b66\u4f4d\u3002 \u4e3b\u8981\u7ecf\u5386 2000.12-2001.11\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u6210\u90fd\u6709\u673a\u5316\u5b66\u7814\u7a76\u6240\uff0c\u52a9\u7406\u7814\u7a76\u5458\uff1b 2000.12-2001.11\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u6210\u90fd\u6709\u673a\u5316\u5b66\u7814\u7a76\u6240\uff0c\u526f\u7814\u7a76\u5458 2001.12-2005.12\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u6210\u90fd\u6709\u673a\u5316\u5b66\u7814\u7a76\u6240\uff0c\u7814\u7a76\u5458\uff0c\u535a\u58eb\u751f\u5bfc\u5e08\uff0c\u5148\u540e\u4efb\u4e0d\u5bf9\u79f0\u5408\u6210\u548c\u624b\u6027\u6280\u672f\u56db\u5ddd\u7701\u91cd\u70b9\u5b9e\u9a8c\u5ba4\u5e38\u52a1\u526f\u4e3b\u4efb\uff0c\u4e3b\u4efb\uff1b 2003.10-2004.09\uff0c\u5fb7\u56fd\u6155\u5c3c\u9ed1\u5927\u5b66(Ludwig-Maximilians-Universit\u00e4t M\u00fcnchen) \u6709\u673a\u5316\u5b66\u7814\u7a76\u6240, \u6d2a\u5821\u5b66\u8005\uff0c\u8bbf\u95ee\u6559\u6388\uff1b 2006.01-\u81f3\u4eca\uff0c\u4e2d\u56fd\u79d1\u5b66\u6280\u672f\u5927\u5b66\u5316\u5b66\u7cfb\uff0c\u5408\u80a5\u5fae\u5c3a\u5ea6\u7269\u8d28\u79d1\u5b66\u56fd\u5bb6\u7814\u7a76\u4e2d\u5fc3\uff0c\u6559\u6388\uff1b 2011.01-\u81f3\u4eca\uff0c\u5408\u80a5\u5fae\u5c3a\u5ea6\u7269\u8d28\u79d1\u5b66\u56fd\u5bb6\u7814\u7a76\u4e2d\u5fc3\u4f4e\u7ef4\u7269\u7406\u4e0e\u5316\u5b66\u7814\u7a76\u90e8\u4e3b\u4efb\u3002 \u7814\u7a76\u9886\u57df \u6709\u673a\u5c0f\u5206\u5b50\u548c\u91d1\u5c5e\u201c\u534f\u540c\u201d\u6216\u201c\u63a5\u529b\u201d\u50ac\u5316\u7684\u53cd\u5e94\uff0c\u53d1\u5c55\u6784\u5efa\u590d\u6742\u7ed3\u6784\u624b\u6027\u5206\u5b50\u7684\u6b65\u9aa4\u7ecf\u6d4e\u6027\u53cd\u5e94\uff0c\u7814\u7a76\u5f71\u54cd\u534f\u540c\u548c\u63a5\u529b\u50ac\u5316\u7684\u89c4\u5f8b \u53d1\u5c55\u4e32\u8054\u53cd\u5e94\u3001\u73af\u52a0\u6210\u53cd\u5e94\u4ee5\u53ca\u4e0d\u5bf9\u79f0\u591a\u7ec4\u5206\u53cd\u5e94\u7b49\uff0c\u63a2\u7d22\u5feb\u901f\u6784\u5efa\u7ed3\u6784\u591a\u6837\u6027\u7684\u624b\u6027\u751f\u7406\u6d3b\u6027\u5206\u5b50\u7684\u5408\u6210\u65b9\u6cd5 \u60f0\u6027\u78b3\u6c22\u952e\u7684\u4e0d\u5bf9\u79f0\u5b98\u80fd\u56e2\u5316 \u50ac\u5316\u4e0d\u5bf9\u79f0\u5408\u6210\u590d\u6742\u5929\u7136\u751f\u7269\u78b1\u548c\u751f\u7406\u6d3b\u6027\u5206\u5b50 \u8bba\u6587\u6982\u8981 \u4ee5N,N-\u4e8c\u5f02\u4e19\u57fa\u80fa\u57fa\u5f02\u4e01\u786b\u4ee3\u9170\u80fa2a\u548c\u82ef\u787c\u9178\u4e3a\u6a21\u677f\u5e95\u7269\uff0c\u4f5c\u8005\u5bf9\u5404\u79cd\u53cd\u5e94\u6761\u4ef6\u8fdb\u884c\u53cd\u590d\u7b5b\u9009\uff0c\u786e\u5b9a\u6700\u4f73\u6761\u4ef6\u4e3a(Table 1)\uff1aN2\u4fdd\u62a4\u6761\u4ef6\u4e0b\uff0c5 mol\uff05Pd2(dba)3\u548c12 mol\uff05CPA1\u4e3a\u50ac\u5316\u5242\uff0c2 equiv 1,4-BQ\u4e3a\u6c27\u5316\u5242\uff0c 3 \u00c5\u5206\u5b50\u7b5b\u4e3a\u6dfb\u52a0\u7269\uff0ctAmylOH\u4e3a\u6eb6\u5242\uff0c\u572860 oC\u6761\u4ef6\u4e0b\u53cd\u5e9412 h\uff0c\u80fd\u4ee591%\u7684\u6536\u7387\u548c97%\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230\u76f8\u5e94\u4ea7\u72693a\u3002 Table 1. \u6761\u4ef6\u7b5b\u9009 \u5728\u6700\u4f18\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u5bf9\u82b3\u57fa\u787c\u9178\u7684\u5e95\u7269\u8303\u56f4\u8fdb\u884c\u4e86\u8003\u5bdf\u3002\u5404\u79cd\u5438\u7535\u5b50\u6216\u7ed9\u7535\u5b50\u53d6\u4ee3\u7684\u82ef\u787c\u9178\u5747\u80fd\u8f83\u597d\u7684\u9002\u5e94\u53cd\u5e94\u6761\u4ef6\uff0c\u80fd\u4ee5\u826f\u597d\u81f3\u4f18\u79c0\u7684\u6536\u7387\u53ca\u4f18\u79c0\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230\u76f8\u5e94\u4ea7\u7269\uff0c\u4f46\u7532\u57fa\u787c\u9178\u53ea\u80fd\u4ee518%\u7684\u6536\u7387\u548c56%\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230\u76f8\u5e94\u4ea7\u7269\u3002\u7d27\u63a5\u7740\uff0c\u4f5c\u8005\u5bf9\u5f02\u4e01\u786b\u4ee3\u9170\u80fa\u8fdb\u884c\u4e86\u52a8\u529b\u5b66\u62c6\u5206\u8fc7\u7a0b\u3002\u901a\u8fc7\u7b80\u5355\u7684\u6761\u4ef6\u4f18\u5316\u786e\u5b9aCPA6\u4e3a\u6700\u4f18\u50ac\u5316\u5242\u3002\u5728\u8be5\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u5404\u79cd\u53d6\u4ee3\u7684\u5f02\u4e01\u786b\u4ee3\u9170\u80fa\u90fd\u80fd\u4ee5\u4e2d\u7b49\u7684\u6536\u7387\u548c\u826f\u597d\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230\u76f8\u5e94\u7684\u4e8c\u82b3\u57fa\u4ea7\u7269\uff0c\u540c\u65f6\uff0c\u53ef\u4ee5\u56de\u6536\u91cd\u8981\u7684\u624b\u6027\u5f02\u4e01\u786b\u4ee3\u9170\u80fa\u5316\u5408\u7269\u3002 \u4e3a\u4e86\u8bc1\u660e\u53cd\u5e94\u7684\u5e94\u7528\u6f5c\u529b\uff0c\u4f5c\u8005\u8fdb\u884c\u4e86\u4e00\u7cfb\u5217\u884d\u751f\u53cd\u5e94(Scheme 2)\u3002\u5728\u6700\u4f18\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c2a\u53ef\u4e0e4-\u6c2f\u82ef\u787c\u9178\u53d1\u751f\u6c27\u5316C\u2012H\u5076\u8054\u53cd\u5e94\uff0c\u80fd\u4ee592\uff05\u7684\u6536\u7387\u548c95\uff05\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230(S)-3f\u3002(S)-3f\u901a\u8fc7\u7b80\u5355\u7684\u5316\u5b66\u4fee\u9970\u5373\u53efS1P\u62ee\u6297\u5242\u3002\u540c\u65f6\uff0c\u4f5c\u8005\u901a\u8fc7MS\u5206\u6790\u548cDFT\u8ba1\u7b97\u5206\u6790\u8bc1\u5b9e\u4e86\u5927\u4f4d\u963b\u53d6\u4ee3\u7684\u624b\u6027\u78f7\u9178\u662f\u53cd\u5e94\u4ea7\u7269\u7684\u9ad8\u5bf9\u6620\u9009\u62e9\u6027\u7684\u5fc5\u8981\u6761\u4ef6\u3002 Scheme 2. \u884d\u751f\u53cd\u5e94 \u8bba\u6587\u603b\u7ed3\u8bc4\u4ef7 \u4e2d\u56fd\u79d1\u5b66\u6280\u672f\u5927\u5b66\u9f9a\u6d41\u67f1\u56e2\u961f\u6210\u529f\u62a5\u9053\u4e86\u9996\u4f8bPd(II)\u50ac\u5316N,N-\u4e8c\u5f02\u4e19\u57fa\u80fa\u57fa\u5f02\u4e01\u786b\u4ee3\u9170\u80fa\u7684\u4e0d\u5bf9\u79f0\u03b2-C(sp3)-H\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\uff0c\u80fd\u4ee5\u4f18\u79c0\u7684\u6536\u7387\u548c\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230\u4e00\u7cfb\u5217\u624b\u6027\u03b2-\u82b3\u57fa\u5f02\u4e01\u9170\u80fa\u3002\u5bc6\u5ea6\u6cdb\u51fd\u7406\u8bba\uff08DFT\uff09\u8ba1\u7b97\u663e\u793aN\u53d6\u4ee3\u57fa\u53d8\u5927\uff0cC\u2013H\u952e\u65ad\u88c2\u7684\u4f4d\u70b9\u8d8a\u63a5\u8fd1\u786b\u4ee3\u9170\u80fa\u3002 \u53c2\u8003\u6587\u732e [1] (a) Jain, P.; Verma, P.; Xia, G.; Yu, J.-Q. 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