{"id":15659,"date":"2017-09-15T05:49:42","date_gmt":"2017-09-14T21:49:42","guid":{"rendered":"\/\/www.gsbet888.com\/?p=15659"},"modified":"2019-08-02T18:52:45","modified_gmt":"2019-08-02T10:52:45","slug":"%e8%81%94%e7%83%af%e4%b8%b2%e8%81%94%e5%8f%8d%e5%ba%94%e5%90%88%e6%88%90%e4%ba%8c%e5%a5%8e%e7%83%b7%e5%92%8c%e4%b8%89%e5%a5%8e%e7%83%b7","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2017\/09\/%e8%81%94%e7%83%af%e4%b8%b2%e8%81%94%e5%8f%8d%e5%ba%94%e5%90%88%e6%88%90%e4%ba%8c%e5%a5%8e%e7%83%b7%e5%92%8c%e4%b8%89%e5%a5%8e%e7%83%b7.html","title":{"rendered":"\u8054\u70ef\u4e32\u8054\u53cd\u5e94\u5408\u6210\u4e8c\u594e\u70f7\u548c\u4e09\u594e\u70f7"},"content":{"rendered":"<p style=\"text-align: left\"><strong>\u672c\u6587\u6295\u7a3f\u4f5c\u8005\uff1a\u5b59\u82cf\u8d5f<\/strong><\/p>\n<p>&nbsp;<\/p>\n<p>\u5728\u5929\u7136\u7269\u4e2d\uff0c\u5177\u6709\u591a\u4e2a\u8fde\u7eed\u624b\u6027\u4e2d\u5fc3\u7684\u591a\u73af\u5929\u7136\u4ea7\u7269\u975e\u5e38\u591a\uff08Fig.1\uff09\uff0c\u8fd9\u4e9b\u7ed3\u6784\u5e38\u5e38\u662f\u5408\u6210\u5de5\u4f5c\u4e2d\u7684\u96be\u70b9\u3002\u5728\u6b64\u524d\uff0cCurran\u8bfe\u9898\u7ec4\u66fe\u62a5\u9053\u8fc7\u4e00\u79cd\u9521\u70f7\u5f15\u53d1\u7684\u81ea\u7531\u57fa\u4e32\u8054\u73af\u5316\u53cd\u5e94\u751f\u6210\u4e09\u4e2a\u5e76\u73af\u5316\u5408\u7269(ref.1)\uff0c\u5176\u8fc7\u7a0b\u662f\u5f15\u53d1\u5242<em><sup>n<\/sup><\/em>Bu<sub>3<\/sub>SnH\u5c06\u7094\u8f6c\u5316\u6210\u70ef\u70c3\u81ea\u7531\u57fa\uff0c\u518d\u7ecf\u8fc7\u4e24\u6b21\u6210\u73af\u5f97\u5230\u5177\u6709\u56db\u4e2a\u8fde\u7eed\u624b\u6027\u4e2d\u5fc3\u76845,5,5-\u4e09\u73af\u7ed3\u6784\u9aa8\u67b6\uff08Fig.2-eq.1\uff09\u3002\u6b64\u5916Krische\u8bfe\u9898\u7ec4\u57282005\u5e74\u4e5f\u5f00\u53d1\u8fc7\u4e00\u79cd\u5206\u5b50\u5185[3+2]\u73af\u52a0\u6210\u53cd\u5e94(ref.2)\u6210\u5f62\u62105,5-\u4e8c\u5e76\u73af\u9aa8\u67b6\uff08Fig.2-eq.2\uff09\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/1-23.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15710 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/1-23.png\" alt=\"\" width=\"478\" height=\"251\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/1-23.png 478w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/1-23-300x158.png 300w\" sizes=\"(max-width: 478px) 100vw, 478px\" \/><\/a><\/p>\n<p>&nbsp;<\/p>\n<p style=\"text-align: center\">Figure1<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/2-31.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15711 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/2-31.png\" alt=\"\" width=\"535\" height=\"375\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/2-31.png 535w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/2-31-300x210.png 300w\" sizes=\"(max-width: 535px) 100vw, 535px\" \/><\/a><\/p>\n<p style=\"text-align: center\">Figure\u591a\u73af\u841c\u7c7b\u5316\u5408\u7269\u7684\u5408\u6210<\/p>\n<p>\u4e13\u6ce8\u4e8e\u841c\u7c7b\u5929\u7136\u4ea7\u7269\u5168\u5408\u6210\u7684\u6768\u9707\u6559\u6388\u4e0d\u4e45\u524d\u5728<strong><em>OrganicLetter<\/em><\/strong>\u4e0a\u62a5\u9053\u4e86\u4e00\u7bc7(<em>Org.Lett<\/em>.,DOI:10.1021\/acs.orglett.7b01733)\uff0c\u62a5\u9053\u4e86\u4e00\u79cd\u65e0\u91d1\u5c5e\u53c2\u4e0e\u7684\u8054\u70ef\u4e3a\u53cd\u5e94\u5e95\u7269\u751f\u6210\u5177\u6709\u8fde\u7eed\u56db\u4e2a\u624b\u6027\u4e2d\u5fc3\u76845,5-\u4e8c\u5e76\u73af\u7684\u4e0d\u5bf9\u79f0\u53cd\u5e94\u3002\u524d\u4eba\u5f00\u53d1\u7684\u53cd\u5e94\u662f\u7528Br\uff0cPhS\u6216\u662fRSO<sub>2<\/sub>\u81ea\u7531\u57fa\u5f15\u53d1\u53cd\u5e94\u7684\uff0c\u8fd9\u91cc\u8003\u8651\u4f7f\u7528\u82b3\u57fa\u786b\u915a\u5f15\u53d1\u53cd\u5e94\uff0c\u4e8e\u662f\u63d0\u51fa\u4e86\u8bbe\u8ba1\u7684\u53cd\u5e94\u673a\u7406\uff1a<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/3-20.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15712 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/3-20.png\" alt=\"\" width=\"443\" height=\"401\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/3-20.png 443w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/3-20-300x272.png 300w\" sizes=\"(max-width: 443px) 100vw, 443px\" \/><\/a><\/p>\n<p style=\"text-align: center\">Figure3\u63d0\u51fa\u7684\u53ef\u80fd\u7684\u53cd\u5e94\u673a\u7406<\/p>\n<p>\u53cd\u5e94\u8fc7\u7a0b\u4e2d\uff0cABVN\u8131\u53bbN<sub>2<\/sub>\u751f\u6210\u70f7\u57fa\u81ea\u7531\u57fa\uff0c\u81ea\u7531\u57fa\u8fdb\u653b\u786b\u915a\u751f\u6210\u786b\u81ea\u7531\u57fa\uff0c\u786b\u81ea\u7531\u57fa\u4f1a\u503e\u5411\u4e8e\u8054\u70ef\u4e2d\u591a\u53d6\u4ee3\u7684\u78b3\u539f\u5b50\u751f\u6210\u4e2d\u95f4\u4f53<strong>A<\/strong>\uff0c<strong>A<\/strong>\u4e2d\u81ea\u7531\u57fa\u8fdb\u653b\u554a\u03b1,\u03b2-\u4e0d\u9971\u952e\u53d1\u751f5-<em>exo<\/em>-trig\u73af\u5316\u5f97\u5230\u53e6\u4e00\u81ea\u7531\u57fa\u4e2d\u95f4\u4f53<strong>B<\/strong>\uff0c<strong>B<\/strong>\u518d\u6210\u73af\u5f97\u5230\u4eb2\u6838\u7684\u81ea\u7531\u57fa\u4e2d\u95f4\u4f53C\uff0cC\u5f97\u5230\u4e00\u4e2a\u8d28\u5b50\u73af\u5f97\u5230\u4e86\u4ea7\u7269<strong>7<\/strong>\u548c\u751f\u6210ArS\u81ea\u7531\u57fa\u3002<\/p>\n<p>\u4e3a\u4e86\u4f18\u5316\u53cd\u5e94\u6761\u4ef6\uff0c\u63a5\u4e0b\u6765\u8fdb\u884c\u4e86\u53cd\u5e94\u6761\u4ef6\u7684\u7b5b\u9009\u3002\u5f71\u54cd\u53cd\u5e94\u4e3b\u8981\u6709\u53cd\u5e94\u5f15\u53d1\u5242\u7684\u79cd\u7c7b\u548c\u5242\u91cf\u3001\u82b3\u57fa\u786b\u915a\u7684\u79cd\u7c7b\u548c\u5242\u91cf\u3001\u53cd\u5e94\u6eb6\u5242\u548c\u5e95\u7269\u7684\u53d6\u4ee3\u57fa\u51e0\u79cd\u5f71\u54cd\u56e0\u7d20\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/4-19.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15713 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/4-19.png\" alt=\"\" width=\"324\" height=\"115\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/4-19.png 324w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/4-19-300x106.png 300w\" sizes=\"(max-width: 324px) 100vw, 324px\" \/><\/a><\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/5-17.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15714 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/5-17.png\" alt=\"\" width=\"433\" height=\"232\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/5-17.png 433w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/5-17-300x161.png 300w\" sizes=\"(max-width: 433px) 100vw, 433px\" \/><\/a><\/p>\n<p style=\"text-align: center\">Table1\u53cd\u5e94\u6761\u4ef6\u7684\u7b5b\u9009<\/p>\n<p>\u9996\u5148\u662f\u5f15\u53d1\u53cd\u5242\u7684\u7b5b\u9009\uff08Tbl.1\uff09\uff0c\u6d4b\u8bd5\u4e2d\u7684\u6eb6\u5242\u6709\u7532\u82ef\uff0cCCl<sub>4<\/sub>\uff0cDCE\uff0cCH<sub>3<\/sub>CN\uff0c\u540c\u65f6\u6539\u53d8\u5f15\u53d1\u5242\u7684\u79cd\u7c7b\u548c\u5242\u91cfAIBN\/ABVN\uff080.1\/0.2equiv.\uff09\u548c\u786b\u915aPhSH\u7684\u5242\u91cf\uff082\/5equiv.\uff09\uff0c\u591a\u6b21\u8bd5\u9a8c\u4e4b\u540e\u5f97\u5230\u6700\u4f18\u5316\u53cd\u5e94\u6761\u4ef6\uff1aCH<sub>3<\/sub>CN\u4e3a\u6eb6\u5242\uff0c0.2equiv.ABVN\u548c2equiv.PhSH\u505a\u81ea\u7531\u57fa\u5f15\u53d1\u5242\uff0c\u6b64\u6761\u4ef6\u4e0b\u4ea7\u7387\u53ef\u9ad8\u8fbe70%\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/6-14.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15715 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/6-14.png\" alt=\"\" width=\"521\" height=\"580\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/6-14.png 521w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/6-14-269x300.png 269w\" sizes=\"(max-width: 521px) 100vw, 521px\" \/><\/a><\/p>\n<p style=\"text-align: center\">Scheme1\u5e95\u7269\u53d6\u4ee3\u57fa\u5bf9\u8054\u70ef\u7684[3+2]\u53cd\u5e94\u7684\u5f71\u54cd<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/7-10.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15716 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/7-10.png\" alt=\"\" width=\"514\" height=\"448\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/7-10.png 514w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/7-10-300x261.png 300w\" sizes=\"(max-width: 514px) 100vw, 514px\" \/><\/a><\/p>\n<p style=\"text-align: center\">Scheme2\u82b3\u57fa\u786b\u915a\u7684\u7535\u5b50\u6548\u5e94\u5bf9\u53cd\u5e94\u7684\u5f71\u54cd<\/p>\n<p>\u63a5\u4e0b\u6765\u662f\u5e95\u7269\u53d6\u4ee3\u57fa\u548c\u786b\u915a\u4e0a\u53d6\u4ee3\u57fa\u5bf9\u53cd\u5e94\u7684\u5f71\u54cd\u3002<\/p>\n<p>\u8bd5\u9a8c\u540e\u53d1\u73b0\uff0c\u5e95\u7269\u4e0aR<sub>1<\/sub>\u5bf9\u53cd\u5e94\u4ea7\u7387\u7684\u5f71\u54cd\u4e0d\u5927\uff0c\u9664\u4e2a\u522b\u5e95\u7269(<strong>10i<\/strong>\uff0cR<sup>1<\/sup>=Ph)\u5916\uff0c\u53cd\u5e94\u7684\u4ea7\u7387\u5747\u572850-70%\u4e4b\u95f4\uff0c\u8fd9\u4e00\u70b9\u5728\u5408\u6210\u4e0a\u662f\u5f88\u5177\u6709\u6f5c\u5728\u7684\u5229\u7528\u4ef7\u503c\u7684\uff08Schm.1\uff09\u3002<\/p>\n<p>\u800cR<sup>2<\/sup>\u7684\u5f71\u54cd\uff0c\u5728\u6b64\u524d\u6709\u7814\u7a76\u62a5\u9053(ref.3)\uff0cEDG\u4f1a\u5bfc\u81f4PhS-H\u952e\u89e3\u79bb\u80fd\u589e\u52a0\u800c\u4e0d\u5229\u4e8e\u53cd\u5e94\uff0c\u6545EWG\u662f\u6709\u5229\u4e8e\u53cd\u5e94\u7684\uff0c\u5982Schm.2\u6240\u793a\u3002\u5e76\u4e14\u5728\u66ff\u6362\u4e0d\u540c\u79cd\u7c7b\u7684\u786b\u915a\u540e\u53d1\u73b0\uff0c\u5bf9\u4e8e\u76f8\u540c\u7684\u53d6\u4ee3\u57fa\uff0c<em>o<\/em>-\/<em>m<\/em>-\u4e8c\u53d6\u4ee3\u786b\u915a\u7684\u4ea7\u7387\u4e0d\u5982<em>p<\/em>-\u4e8c\u53d6\u4ee3\u786b\u915a\uff0c\u5e76\u4e14\u53d6\u4ee3\u57fa\u4e3aEDG\u6709\u5229\u4e8e\u53cd\u5e94\u4ea7\u7387\u7684\u63d0\u9ad8\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/8-7.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15717 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/8-7.png\" alt=\"\" width=\"441\" height=\"238\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/8-7.png 441w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/8-7-300x162.png 300w\" sizes=\"(max-width: 441px) 100vw, 441px\" \/><\/a><\/p>\n<p style=\"text-align: center\">Scheme3\u4e09\u594e\u70f7\u7684\u5408\u6210<\/p>\n<p>\u6700\u540e\uff0c\u8fd9\u4e2a\u53cd\u5e94\u88ab\u7528\u4e8e\u4ee5\u4e0a\u7684\u53cd\u5e94(Schm.3)\uff0c\u8fd9\u8868\u660e\u5982\u679c\u53cd\u5e94\u5e95\u7269\u73af\u72b6\u662f\u73af\u72b6\u5316\u5408\u7269\uff0c\u90a3\u4e48\u4ea7\u7269\u662f\u53ef\u4ee5\u5f97\u5230\u591a\u73af\u5316\u5408\u7269\u7684\uff0cSchm.3\u4e2d\u7684<strong>12a\/b<\/strong>\u548c<strong>14<\/strong>\u5c31\u5206\u522b\u9ad8\u4ea7\u7387\u7684\u8f6c\u5316\u6210\u4e86<strong>13a\/b<\/strong>\u548c<strong>15<\/strong>\uff0c\u5176\u4e2d<strong>15<\/strong>\u7684ee\u503c\u9ad8\u8fbe92%\u3002\u8fd9\u4e2a\u53cd\u5e94\u5728\u5168\u5408\u6210\u4e2d\u7684\u5e94\u7528\u73b0\u5728\u6b63\u5728\u6768\u9707\u6559\u6388\u7684\u8bfe\u9898\u7ec4\u4e2d\u5c55\u5f00(ref.4)\uff0c\u6211\u4eec\u671f\u5f85\u7cbe\u5f69\u7684\u5168\u5408\u6210\uff01<\/p>\n<p>&nbsp;<\/p>\n<h4><b>\u53c2\u8003\u6587\u732e<\/b><\/h4>\n<ol>\n<li>(a)\u00a0<em>J. Am. Chem. Soc.<\/em> <strong>1985<\/strong>, <em>107<\/em>, 1448. DOI: 10.1021\/ja00291a077\u00a0 (b)\u00a0<em>Tetrahedron Lett<\/em>. <strong>1985,<\/strong> <em>26<\/em>, 4991. DOI: 10.1016\/S0040-4039(01)80834-0<\/li>\n<li>(a)\u00a0<em>Org. Lett.<\/em> <strong>2007<\/strong>, <em>9<\/em>, 3069. DOI: 10.1021\/ol071181d (b)\u00a0<em>J. Am. Chem. Soc.<\/em> <strong>2015<\/strong>, <em>137<\/em>, 4587. DOI: 10.1021\/jacs.5b01985<\/li>\n<li>(a)<em>Acc. Chem. Res<\/em>. <strong>2004<\/strong>, <em>37<\/em>, 334. DOI: 10.1021\/ar010010k\u00a0(b)<em>J. Org. Chem<\/em>. <strong>1996<\/strong>, <em>61<\/em>, 8312. DOI: 10.1021\/jo961301n\u3000(c)\u00a0<em>J. Am. Chem. Soc<\/em>.<strong> 1994<\/strong>, <em>116<\/em>, 6605. DOI: 10.1021\/ja00094a015<\/li>\n<li><em>Angew. Chem., Int. Ed<\/em>. <strong>2017<\/strong>, <em>56<\/em>, 8254. DOI: 10.1002\/anie.201704492<\/li>\n<\/ol>\n<p>&nbsp;<\/p>\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":"\u672c\u6587\u6295\u7a3f\u4f5c\u8005\uff1a\u5b59\u82cf\u8d5f &nbsp; \u5728\u5929\u7136\u7269\u4e2d\uff0c\u5177\u6709\u591a\u4e2a\u8fde\u7eed\u624b\u6027\u4e2d\u5fc3\u7684\u591a\u73af\u5929\u7136\u4ea7\u7269\u975e\u5e38\u591a\uff08Fig.1\uff09\uff0c\u8fd9\u4e9b\u7ed3\u6784\u5e38\u5e38\u662f\u5408\u6210\u5de5\u4f5c\u4e2d\u7684\u96be\u70b9\u3002\u5728\u6b64\u524d\uff0cCurran\u8bfe\u9898\u7ec4\u66fe\u62a5\u9053\u8fc7\u4e00\u79cd\u9521\u70f7\u5f15\u53d1\u7684\u81ea\u7531\u57fa\u4e32\u8054\u73af\u5316\u53cd\u5e94\u751f\u6210\u4e09\u4e2a\u5e76\u73af\u5316\u5408\u7269(ref.1)\uff0c\u5176\u8fc7\u7a0b\u662f\u5f15\u53d1\u5242nBu3SnH\u5c06\u7094\u8f6c\u5316\u6210\u70ef\u70c3\u81ea\u7531\u57fa\uff0c\u518d\u7ecf\u8fc7\u4e24\u6b21\u6210\u73af\u5f97\u5230\u5177\u6709\u56db\u4e2a\u8fde\u7eed\u624b\u6027\u4e2d\u5fc3\u76845,5,5-\u4e09\u73af\u7ed3\u6784\u9aa8\u67b6\uff08Fig.2-eq.1\uff09\u3002\u6b64\u5916Krische\u8bfe\u9898\u7ec4\u57282005\u5e74\u4e5f\u5f00\u53d1\u8fc7\u4e00\u79cd\u5206\u5b50\u5185[3+2]\u73af\u52a0\u6210\u53cd\u5e94(ref.2)\u6210\u5f62\u62105,5-\u4e8c\u5e76\u73af\u9aa8\u67b6\uff08Fig.2-eq.2\uff09\u3002 &nbsp; Figure1 Figure\u591a\u73af\u841c\u7c7b\u5316\u5408\u7269\u7684\u5408\u6210 \u4e13\u6ce8\u4e8e\u841c\u7c7b\u5929\u7136\u4ea7\u7269\u5168\u5408\u6210\u7684\u6768\u9707\u6559\u6388\u4e0d\u4e45\u524d\u5728OrganicLetter\u4e0a\u62a5\u9053\u4e86\u4e00\u7bc7(Org.Lett.,DOI:10.1021\/acs.orglett.7b01733)\uff0c\u62a5\u9053\u4e86\u4e00\u79cd\u65e0\u91d1\u5c5e\u53c2\u4e0e\u7684\u8054\u70ef\u4e3a\u53cd\u5e94\u5e95\u7269\u751f\u6210\u5177\u6709\u8fde\u7eed\u56db\u4e2a\u624b\u6027\u4e2d\u5fc3\u76845,5-\u4e8c\u5e76\u73af\u7684\u4e0d\u5bf9\u79f0\u53cd\u5e94\u3002\u524d\u4eba\u5f00\u53d1\u7684\u53cd\u5e94\u662f\u7528Br\uff0cPhS\u6216\u662fRSO2\u81ea\u7531\u57fa\u5f15\u53d1\u53cd\u5e94\u7684\uff0c\u8fd9\u91cc\u8003\u8651\u4f7f\u7528\u82b3\u57fa\u786b\u915a\u5f15\u53d1\u53cd\u5e94\uff0c\u4e8e\u662f\u63d0\u51fa\u4e86\u8bbe\u8ba1\u7684\u53cd\u5e94\u673a\u7406\uff1a Figure3\u63d0\u51fa\u7684\u53ef\u80fd\u7684\u53cd\u5e94\u673a\u7406 \u53cd\u5e94\u8fc7\u7a0b\u4e2d\uff0cABVN\u8131\u53bbN2\u751f\u6210\u70f7\u57fa\u81ea\u7531\u57fa\uff0c\u81ea\u7531\u57fa\u8fdb\u653b\u786b\u915a\u751f\u6210\u786b\u81ea\u7531\u57fa\uff0c\u786b\u81ea\u7531\u57fa\u4f1a\u503e\u5411\u4e8e\u8054\u70ef\u4e2d\u591a\u53d6\u4ee3\u7684\u78b3\u539f\u5b50\u751f\u6210\u4e2d\u95f4\u4f53A\uff0cA\u4e2d\u81ea\u7531\u57fa\u8fdb\u653b\u554a\u03b1,\u03b2-\u4e0d\u9971\u952e\u53d1\u751f5-exo-trig\u73af\u5316\u5f97\u5230\u53e6\u4e00\u81ea\u7531\u57fa\u4e2d\u95f4\u4f53B\uff0cB\u518d\u6210\u73af\u5f97\u5230\u4eb2\u6838\u7684\u81ea\u7531\u57fa\u4e2d\u95f4\u4f53C\uff0cC\u5f97\u5230\u4e00\u4e2a\u8d28\u5b50\u73af\u5f97\u5230\u4e86\u4ea7\u72697\u548c\u751f\u6210ArS\u81ea\u7531\u57fa\u3002 \u4e3a\u4e86\u4f18\u5316\u53cd\u5e94\u6761\u4ef6\uff0c\u63a5\u4e0b\u6765\u8fdb\u884c\u4e86\u53cd\u5e94\u6761\u4ef6\u7684\u7b5b\u9009\u3002\u5f71\u54cd\u53cd\u5e94\u4e3b\u8981\u6709\u53cd\u5e94\u5f15\u53d1\u5242\u7684\u79cd\u7c7b\u548c\u5242\u91cf\u3001\u82b3\u57fa\u786b\u915a\u7684\u79cd\u7c7b\u548c\u5242\u91cf\u3001\u53cd\u5e94\u6eb6\u5242\u548c\u5e95\u7269\u7684\u53d6\u4ee3\u57fa\u51e0\u79cd\u5f71\u54cd\u56e0\u7d20\u3002 Table1\u53cd\u5e94\u6761\u4ef6\u7684\u7b5b\u9009 \u9996\u5148\u662f\u5f15\u53d1\u53cd\u5242\u7684\u7b5b\u9009\uff08Tbl.1\uff09\uff0c\u6d4b\u8bd5\u4e2d\u7684\u6eb6\u5242\u6709\u7532\u82ef\uff0cCCl4\uff0cDCE\uff0cCH3CN\uff0c\u540c\u65f6\u6539\u53d8\u5f15\u53d1\u5242\u7684\u79cd\u7c7b\u548c\u5242\u91cfAIBN\/ABVN\uff080.1\/0.2equiv.\uff09\u548c\u786b\u915aPhSH\u7684\u5242\u91cf\uff082\/5equiv.\uff09\uff0c\u591a\u6b21\u8bd5\u9a8c\u4e4b\u540e\u5f97\u5230\u6700\u4f18\u5316\u53cd\u5e94\u6761\u4ef6\uff1aCH3CN\u4e3a\u6eb6\u5242\uff0c0.2equiv.ABVN\u548c2equiv.PhSH\u505a\u81ea\u7531\u57fa\u5f15\u53d1\u5242\uff0c\u6b64\u6761\u4ef6\u4e0b\u4ea7\u7387\u53ef\u9ad8\u8fbe70%\u3002 Scheme1\u5e95\u7269\u53d6\u4ee3\u57fa\u5bf9\u8054\u70ef\u7684[3+2]\u53cd\u5e94\u7684\u5f71\u54cd Scheme2\u82b3\u57fa\u786b\u915a\u7684\u7535\u5b50\u6548\u5e94\u5bf9\u53cd\u5e94\u7684\u5f71\u54cd \u63a5\u4e0b\u6765\u662f\u5e95\u7269\u53d6\u4ee3\u57fa\u548c\u786b\u915a\u4e0a\u53d6\u4ee3\u57fa\u5bf9\u53cd\u5e94\u7684\u5f71\u54cd\u3002 \u8bd5\u9a8c\u540e\u53d1\u73b0\uff0c\u5e95\u7269\u4e0aR1\u5bf9\u53cd\u5e94\u4ea7\u7387\u7684\u5f71\u54cd\u4e0d\u5927\uff0c\u9664\u4e2a\u522b\u5e95\u7269(10i\uff0cR1=Ph)\u5916\uff0c\u53cd\u5e94\u7684\u4ea7\u7387\u5747\u572850-70%\u4e4b\u95f4\uff0c\u8fd9\u4e00\u70b9\u5728\u5408\u6210\u4e0a\u662f\u5f88\u5177\u6709\u6f5c\u5728\u7684\u5229\u7528\u4ef7\u503c\u7684\uff08Schm.1\uff09\u3002 \u800cR2\u7684\u5f71\u54cd\uff0c\u5728\u6b64\u524d\u6709\u7814\u7a76\u62a5\u9053(ref.3)\uff0cEDG\u4f1a\u5bfc\u81f4PhS-H\u952e\u89e3\u79bb\u80fd\u589e\u52a0\u800c\u4e0d\u5229\u4e8e\u53cd\u5e94\uff0c\u6545EWG\u662f\u6709\u5229\u4e8e\u53cd\u5e94\u7684\uff0c\u5982Schm.2\u6240\u793a\u3002\u5e76\u4e14\u5728\u66ff\u6362\u4e0d\u540c\u79cd\u7c7b\u7684\u786b\u915a\u540e\u53d1\u73b0\uff0c\u5bf9\u4e8e\u76f8\u540c\u7684\u53d6\u4ee3\u57fa\uff0co-\/m-\u4e8c\u53d6\u4ee3\u786b\u915a\u7684\u4ea7\u7387\u4e0d\u5982p-\u4e8c\u53d6\u4ee3\u786b\u915a\uff0c\u5e76\u4e14\u53d6\u4ee3\u57fa\u4e3aEDG\u6709\u5229\u4e8e\u53cd\u5e94\u4ea7\u7387\u7684\u63d0\u9ad8\u3002 Scheme3\u4e09\u594e\u70f7\u7684\u5408\u6210 \u6700\u540e\uff0c\u8fd9\u4e2a\u53cd\u5e94\u88ab\u7528\u4e8e\u4ee5\u4e0a\u7684\u53cd\u5e94(Schm.3)\uff0c\u8fd9\u8868\u660e\u5982\u679c\u53cd\u5e94\u5e95\u7269\u73af\u72b6\u662f\u73af\u72b6\u5316\u5408\u7269\uff0c\u90a3\u4e48\u4ea7\u7269\u662f\u53ef\u4ee5\u5f97\u5230\u591a\u73af\u5316\u5408\u7269\u7684\uff0cSchm.3\u4e2d\u768412a\/b\u548c14\u5c31\u5206\u522b\u9ad8\u4ea7\u7387\u7684\u8f6c\u5316\u6210\u4e8613a\/b\u548c15\uff0c\u5176\u4e2d15\u7684ee\u503c\u9ad8\u8fbe92%\u3002\u8fd9\u4e2a\u53cd\u5e94\u5728\u5168\u5408\u6210\u4e2d\u7684\u5e94\u7528\u73b0\u5728\u6b63\u5728\u6768\u9707\u6559\u6388\u7684\u8bfe\u9898\u7ec4\u4e2d\u5c55\u5f00(ref.4)\uff0c\u6211\u4eec\u671f\u5f85\u7cbe\u5f69\u7684\u5168\u5408\u6210\uff01 &nbsp; \u53c2\u8003\u6587\u732e (a)\u00a0J. Am. Chem. Soc. 1985, 107, 1448. DOI: 10.1021\/ja00291a077\u00a0 (b)\u00a0Tetrahedron Lett. 1985, 26, 4991. DOI: 10.1016\/S0040-4039(01)80834-0 (a)\u00a0Org. Lett. 2007, 9, 3069. DOI: 10.1021\/ol071181d (b)\u00a0J. Am. Chem. Soc. 2015, 137, 4587. DOI: 10.1021\/jacs.5b01985 (a)Acc. Chem. Res. 2004, 37, 334. DOI: 10.1021\/ar010010k\u00a0(b)J. Org. Chem. 1996, 61, 8312. DOI: 10.1021\/jo961301n\u3000(c)\u00a0J. Am. Chem. Soc. 1994, 116, 6605. DOI: 10.1021\/ja00094a015 Angew. Chem., Int. Ed. 2017, 56, 8254. 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