{"id":16620,"date":"2017-10-26T08:37:51","date_gmt":"2017-10-26T00:37:51","guid":{"rendered":"\/\/www.gsbet888.com\/?p=16620"},"modified":"2019-08-02T18:52:25","modified_gmt":"2019-08-02T10:52:25","slug":"%e9%86%87%e4%bd%9c%e4%b8%ba%e7%83%b7%e5%9f%ba%e5%8c%96%e8%af%95%e5%89%82%ef%bc%81%e6%9d%82%e8%8a%b3%e7%8e%af%e7%9a%84c-h%e7%83%b7%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\/2017\/10\/%e9%86%87%e4%bd%9c%e4%b8%ba%e7%83%b7%e5%9f%ba%e5%8c%96%e8%af%95%e5%89%82%ef%bc%81%e6%9d%82%e8%8a%b3%e7%8e%af%e7%9a%84c-h%e7%83%b7%e5%9f%ba%e5%8c%96.html","title":{"rendered":"\u9187\u4f5c\u4e3a\u70f7\u57fa\u5316\u8bd5\u5242\uff01\u6742\u82b3\u73af\u7684C-H\u70f7\u57fa\u5316"},"content":{"rendered":"<p><strong>\u4eca\u5929\u4ecb\u7ecd\u7684\u662f2\u5e74\u524d\u7684\u7bc7\u6587\u7ae0\uff0c2015\u5e74\u3001\u666e\u6797\u65af\u987f\u5927\u5b66\u7684\u30fb<a href=\"\/\/www.gsbet888.com\/chemists\/2014\/11\/post-3283.html\">D. W. C. MacMillan<\/a>\u3001\u5229\u7528\u6c22\u8f6c\u79fb\u50ac\u5316\u5242\uff08HAT\uff09\u4e0e<a href=\"\/\/www.gsbet888.com\/reactions\/2017\/05\/\u53ef\u89c1\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u5242-visible-light-photoredox-catalyst.html\">\u53ef\u89c1\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u5242<\/a>\u8fdb\u884c\u7ec4\u5408\u4f7f\u7528\uff0c\u5728\u6e29\u548c\u6761\u4ef6\u4e0b\u6210\u529f\u5b9e\u73b0\u628a\u9187\u5316\u5408\u7269\u4f5c\u4e3a\u70f7\u57fa\u5316\u8bd5\u5242\u5bf9\u6742\u82b3\u73af\u8fdb\u884cC-H\u70f7\u57fa\u5316\u53cd\u5e94\u3002\u8be5\u65b9\u6cd5\u53ef\u4ee5\u9002\u7528\u4e8e\u533b\u836f\u54c1\u7684<a href=\"\/\/www.gsbet888.com\/\u5316\u5b66\u6742\u8bb0\/2017\/04\/\u5408\u6210\u540e\u671f\u591a\u6837\u5316\u6cd5-late-stage-diversification.html\">Late-Stage\u5b98\u80fd\u56e2\u5316<\/a>\u3002<\/strong><\/p>\n<blockquote><p>\u201cAlcohols as alkylating agents in heteroarene C\u2013H functionalization\u201d<br \/>\nJin, J.; MacMillan, D. W. C.*\u00a0<em>Nature\u00a0<\/em><strong>2015<\/strong>, <em>525<\/em>, 87. doi:<a href=\"http:\/\/dx.doi.org\/10.1038\/nature14885\">10.1038\/nature14885<\/a><\/p><\/blockquote>\n<h4><span id=\"more-53176\"><\/span>\u8bfe\u9898\u8bbe\u5b9a<\/h4>\n<p>\u505a\u836f\u7269\u5408\u6210\u7684\u4eba\u90fd\u77e5\u9053\uff0c\u5373\u4f7f\u662f\u4e00\u4e2a\u5c0f\u5c0f\u7684\u7532\u57fa\u7684\u53d8\u5316\uff0c\u836f\u7269\u8868\u73b0\u51fa\u7684\u6d3b\u6027\u7b49\u90fd\u4f1a\u6709\u663e\u8457\u7684\u53d8\u5316\uff0c\u56e0\u6b64\u6742\u82b3\u73af\u7684\u70f7\u57fa\u7684\u76f4\u63a5\u5bfc\u5165\u6cd5\u5728\u5e94\u7528\u8fd9\u5757\u662f\u975e\u5e38\u91cd\u8981\u7684\u3002\u4f46\u662f\uff0c\u5e38\u89c4\u65b9\u6cd5\uff0c\u901a\u5e38\u90fd\u9700\u8981\u4f7f\u7528\u5f53\u91cf\u7684\u5f3a\u6c27\u5316\u5242\uff0c\u5e76\u4e14\u9700\u8981\u52a0\u70ed\u751f\u6210\u70f7\u57fa\u81ea\u7531\u57fa\uff0c\u5728\u539f\u5b50\u7ecf\u6d4e\u4e0e\u73af\u5883\u8c03\u548c\u6027\u4e0a\u4e0d\u5177\u6709\u4f18\u52bf\u3002\u56e0\u6b64\u5982\u4f55\u5f00\u53d1\u51fa\u4e00\u79cd\u6bd4\u8f83\u9ad8\u6548\u7684\uff0c\u53ef\u4ee5\u50ac\u5316\u8fdb\u884c\u7684\u70f7\u57fa\u5316\u53cd\u5e94\u662f\u4e00\u4e2a\u96be\u9898\uff0c\u5e76\u4e14\u76f4\u63a5\u70f7\u57fa\u5316\u4e5f\u53ef\u4ee5\u5e94\u7528\u4e8eLate-Stage\u5b98\u80fd\u56e2\u5316\uff0c\u8fdb\u884c\u65b0\u7684lead 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300w\" sizes=\"(max-width: 400px) 100vw, 400px\" \/><\/p>\n<p style=\"text-align: center\">\u6458\u81ea\u539f\u8bba\u6587<\/p>\n<p>\u4f5c\u8005\u4e5f\u662f\u6536\u5230\u8fd9\u4e2a\u751f\u6e90\u5408\u6210\u7684\u542f\u53d1\uff0c\u8bbe\u8ba1\u51fa\u4ee5alcohol\u4e3a\u539f\u6599\u751f\u6210alkyl radical\u540e\uff0c\u5bf9\u542b\u6709\u6742\u539f\u5b50\u7684\u82b3\u70c3\u8fdb\u884c\u70f7\u57fa\u5316\u540e\uff0c\u5f15\u53d1SCS\uff0c\u5207\u65adC-O\u952e\u5c31\u53ef\u4ee5\u5b9e\u73b0\u70f7\u57fa\u5316\u8fd9\u4e00\u601d\u8def\u3002\u800cMacmillan\u7ec4\u4ee5\u53ef\u89c1\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u5242\u50ac\u5316\u7684\u81ea\u7531\u57fa\u53cd\u5e94\u6210\u540d\uff0c\u56e0\u6b64\u8be5\u601d\u8def\u4e5f\u662f\u8fd0\u7528\u4ee5\u5f80\u7c7b\u4f3c\u7684\u65b9\u6cd5\uff0c\u5728\u6e29\u548c\u6761\u4ef6\u4e0b\uff0c\u901a\u8fc7\u4ee5\u4e0b\u8bbe\u8ba1\u7684\u50ac\u5316\u5faa\u73af\u8fdb\u884c\u53cd\u5e94\u5f00\u53d1\u3002<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-16623 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/10\/2017-10-15_12h07_34-e1508041571157.png\" alt=\"\" width=\"400\" height=\"458\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/10\/2017-10-15_12h07_34-e1508041571157.png 400w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/10\/2017-10-15_12h07_34-e1508041571157-262x300.png 262w\" sizes=\"(max-width: 400px) 100vw, 400px\" \/><\/p>\n<p style=\"text-align: center\">\u5f15\u7528\u4e8e\u539f\u8bba\u6587<\/p>\n<p>\u800c\u5728\u8fd9\u4e2a\u4f53\u7cfb\u4e2d\u6bd4\u8f83\u5173\u952e\u7684\u662f\u4f53\u7cfb\u4e2d\u751f\u6210\u7684\u786b\u81ea\u7531\u57fa\u5bf9alcohol\u7684C-H\u8fdb\u884c\u62d4\u6c22\u8fd9\u4e00\u8fc7\u7a0b\uff0c\u751f\u6210\u7684\u9187\u7684\u03b1\u78b3\u81ea\u7531\u57fa<strong>8<\/strong>\u518d\u4e0e\u8d28\u5b50\u5316\u7684\u6742\u82b3\u73af\u8fdb\u884c\u81ea\u7531\u57fa\u52a0\u6210\u751f\u6210\u4e2d\u95f4\u4f53<strong>9<\/strong>\uff0c\u63a5\u7740\u5f15\u53d1SCS\u8fdb\u884c\u8131\u6c34\u5f97\u5230\u4ea7\u7269\u3002<\/p>\n<p>MacMillan\u5728\u540c\u5e74\uff0c\u8fd8\u62a5\u9053\u4e86\u8fd0\u7528\u53ef\u89c1\u5149\u50ac\u5316\u5242\u9a71\u52a8\u7684Minisci\u53cd\u5e94[2]\uff0c\u867d\u7136\u4e0e\u8fd9\u7bc7\u770b\u4f3c\u76f8\u4f3c\uff0c\u4f46\u662f\u5176\u5b9e\u5927\u4e0d\u76f8\u540c\uff0c\u533a\u522b\u5728\u4e8e\u8fd9\u7bc7\u4e2d\u7684\u70f7\u57fa\u81ea\u7531\u57fa\u52a0\u6210\u540e\uff0c\u8fd0\u7528\u4e86SCS\u7684C-O\u952e\u5207\u65ad\u53cd\u5e94\u3002<\/p>\n<h4>\u5047\u8bbe\u7684\u6709\u6548\u6027\u9a8c\u8bc1<\/h4>\n<h5>\u2460SCS\u8fc7\u7a0b\u4ecb\u5bfc\u7684\u9a8c\u8bc1<\/h5>\n<p>\u539f\u8bba\u6587\u4f5c\u8005\u8fdb\u884c\u4e86\u4e0b\u56fe\u6240\u793a\u7684radical\u6355\u6349\u5b9e\u9a8c\uff0c\u5149\u3001\u5149\u50ac\u5316\u5242\u3001\u8fd8\u539f\u5242\uff08Bu<sub>3<\/sub>N\uff09\u3001\u9178\uff08HCO<sub>2<\/sub>H\u6216\u8005\u662fTsOH\uff09\u5b58\u5728\u4e0b\uff0c\u89c2\u6d4b\u5230\u4e86C-O\u952e\u65ad\u88c2\uff0c\u4e0e\u5f02\u55b9\u5549\u82c4\u57fa\u4f4d\u7f6e\u78b3\u81ea\u7531\u57fa\u7684\u751f\u6210\u8fd9\u4e00\u7ed3\u679c\u652f\u6301\u4e86\u5176\u5047\u8bf4\u3002<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-16624 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/10\/alcohol_alkylation_HetAr_4-e1508041646898.png\" alt=\"\" width=\"426\" height=\"282\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/10\/alcohol_alkylation_HetAr_4-e1508041646898.png 426w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/10\/alcohol_alkylation_HetAr_4-e1508041646898-300x199.png 300w\" sizes=\"(max-width: 426px) 100vw, 426px\" \/><\/p>\n<h5>\u2461\u53cd\u5e94\u673a\u7406\u7684\u8ba8\u8bba<\/h5>\n<ul>\n<li>\u5149\u6fc0\u53d1\u7684Ir\uff08III\uff09\u88ab\u8d28\u5b50\u5316\u7684\u6742\u82b3\u65cf\u73af\u6dec\u706d\u3002\u53e6\u4e00\u65b9\u9762\uff0c\u5b83\u4e0d\u88ab\u786b\u9187\u6216\u975e\u8d28\u5b50\u5316\u6742\u82b3\u70c3\u6dec\u706d\u3002\u8fd9\u8868\u660e\u53cd\u5e94\u4e2d\u7ecf\u5386\u4e86\u6c27\u5316\u731d\u706d\u8fc7\u7a0b\u3002<\/li>\n<li>\u4ece\u6c27\u5316\u8fd8\u539f\u7535\u4f4d\u503c\u53ef\u4ee5\u770b\u51fa\u3001Ir(IV)\u6c27\u5316\u786b\u9187\u7684\u8fc7\u7a0b\u662f\u5408\u7406\u7684\u3002\uff08Ir\uff08\u2163\uff09\u306fE<sub>1\/2<\/sub>= +1.21 V(vs SCE in MeCN)\u3001\u786b\u9187E<sub>1\/2<\/sub> = +0.85 V(vs SCE in MeCN)\uff09\u3002<\/li>\n<li>\u7531\u4e8e\u7532\u9187\u7684BDE\uff08\u03b1C-H\uff09\uff1d96 kcal\/mol\u3001\u786b\u9187\u7684BDE\uff08S-H\uff09\uff1d85 kcal\/mol\uff0c\u867d\u7136\u5f3a\u5ea6\u4e0a\u770b\u4f3c\u5e76\u4e0d\u5408\u7406\uff0c\u4f46\u662f\u4f5c\u8005\u4e3b\u5f20\u8fd9\u662f\u7531\u4e8epolarity effect\u8fdb\u884c\u65ad\u952e\u7684\u3002<\/li>\n<li>\u53ef\u89c1\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u5242\uff0c\u786b\u9187\uff0c\u5149\uff0c\u9178\u7f3a\u4e00\u4e0d\u53ef\u3002<\/li>\n<\/ul>\n<h5>\u2462\u5e95\u7269\u7684\u9002\u7528\u6027\u8ba8\u8bba<\/h5>\n<p>\u7532\u9187\u7528\u91cf\u4e3a\u6eb6\u5242\u91cf\uff0c\u5176\u4ed6\u7684\u9187\u539f\u6599\u53ea\u9700\u898110\u5f53\u91cf\u5373\u53ef\u3002\u6839\u636e\u5e95\u7269\u7684\u4e0d\u540c\uff0c\u786b\u9187\u7684\u9009\u7528\u4e0e\u66f4\u6539\u4e5f\u662f\u6709\u5fc5\u8981\u7684\u3002\u5728\u56db\u6c22\u544b\u5583\u578b\u4e59\u919a\u7684\u60c5\u51b5\u4e0b\uff0c\u5373\u4f7f\u5728\u4e0e\u4e00\u7ea7\u9187\u5171\u5b58\u7684\u60c5\u51b5\u4e0b\uff0c\u4e5f\u662f\u919a\u7684\u03b1\u4f4d\u7684C-H\u4f18\u5148\u88ab\u62d4\u6389\uff0c\u8fdb\u884c\u5f00\u73af\u53cd\u5e94\u3002\u8be5\u65b9\u6cd5\u53ef\u4ee5\u7528\u4e8e\u533b\u836f\u54c1\u7684Late-Stage\u70f7\u57fa\u5316\u53cd\u5e94\u3002<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-16625 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/10\/alcohol_alkylation_HetAr_5-e1508041810689.png\" alt=\"\" width=\"500\" height=\"485\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/10\/alcohol_alkylation_HetAr_5-e1508041810689.png 500w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/10\/alcohol_alkylation_HetAr_5-e1508041810689-300x291.png 300w\" sizes=\"(max-width: 500px) 100vw, 500px\" \/><\/p>\n<h4>\u9700\u8981\u6539\u5584\u7684\u70b9<\/h4>\n<ul>\n<li>alcohol\u7684\u4f7f\u7528\u91cf\u4e3a\u6eb6\u5242\u91cf\u6216\u800510\u500d\u5f53\u91cf\uff0c\u662f\u5426\u80fd\u591f\u51cf\u5c11\u7528\u91cf\uff1f\u6bd4\u5982\u901a\u8fc7\u4f7f\u7528\u5f3a\u529b\u7684HAT\u50ac\u5316\u5242\u662f\u5426\u80fd\u591f\u5b9e\u73b0?<\/li>\n<\/ul>\n<h4>\u53c2\u8003\u6587\u732e<\/h4>\n<ol>\n<li>Wessig, P.; Muehling, O. <em>Eur. J. Org. Chem.<\/em> <strong>2007<\/strong>, 2219. DOI: <a href=\"http:\/\/dx.doi.org\/10.1002\/ejoc.200600915\">10.1002\/ejoc.200600915<\/a><\/li>\n<li>Jin, J.; MacMillan, D. W. C.<em> Angew. Chem. Int. Ed.<\/em> <strong>2015<\/strong>, <em>54<\/em>, 1565. DOI: <a href=\"http:\/\/dx.doi.org\/10.1002\/anie.201410432\">10.1002\/anie.201410432<\/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":"\u4eca\u5929\u4ecb\u7ecd\u7684\u662f2\u5e74\u524d\u7684\u7bc7\u6587\u7ae0\uff0c2015\u5e74\u3001\u666e\u6797\u65af\u987f\u5927\u5b66\u7684\u30fbD. W. C. MacMillan\u3001\u5229\u7528\u6c22\u8f6c\u79fb\u50ac\u5316\u5242\uff08HAT\uff09\u4e0e\u53ef\u89c1\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u5242\u8fdb\u884c\u7ec4\u5408\u4f7f\u7528\uff0c\u5728\u6e29\u548c\u6761\u4ef6\u4e0b\u6210\u529f\u5b9e\u73b0\u628a\u9187\u5316\u5408\u7269\u4f5c\u4e3a\u70f7\u57fa\u5316\u8bd5\u5242\u5bf9\u6742\u82b3\u73af\u8fdb\u884cC-H\u70f7\u57fa\u5316\u53cd\u5e94\u3002\u8be5\u65b9\u6cd5\u53ef\u4ee5\u9002\u7528\u4e8e\u533b\u836f\u54c1\u7684Late-Stage\u5b98\u80fd\u56e2\u5316\u3002 \u201cAlcohols as alkylating agents in heteroarene C\u2013H functionalization\u201d Jin, J.; MacMillan, D. W. C.*\u00a0Nature\u00a02015, 525, 87. doi:10.1038\/nature14885 \u8bfe\u9898\u8bbe\u5b9a 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Wessig, P.; Muehling, O. Eur. J. Org. Chem. 2007, 2219. DOI: 10.1002\/ejoc.200600915 Jin, J.; MacMillan, D. W. C. Angew. Chem. Int. Ed. 2015, 54, 1565. 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