{"id":25048,"date":"2019-04-16T08:00:27","date_gmt":"2019-04-16T00:00:27","guid":{"rendered":"\/\/www.gsbet888.com\/?p=25048"},"modified":"2019-04-14T23:20:07","modified_gmt":"2019-04-14T15:20:07","slug":"%e9%85%8d%e4%bd%8d%e8%af%b1%e5%af%bc%e5%af%b9%e7%a2%b3%e6%ad%a3%e7%a6%bb%e5%ad%90%e7%ab%8b%e4%bd%93%e9%80%89%e6%8b%a9%e6%80%a7%ef%bc%9a%e5%a4%96%e6%b6%88%e6%97%8b%e4%b8%89%e7%ba%a7%e9%86%87%e7%9a%84","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2019\/04\/%e9%85%8d%e4%bd%8d%e8%af%b1%e5%af%bc%e5%af%b9%e7%a2%b3%e6%ad%a3%e7%a6%bb%e5%ad%90%e7%ab%8b%e4%bd%93%e9%80%89%e6%8b%a9%e6%80%a7%ef%bc%9a%e5%a4%96%e6%b6%88%e6%97%8b%e4%b8%89%e7%ba%a7%e9%86%87%e7%9a%84.html","title":{"rendered":"\u914d\u4f4d\u8bf1\u5bfc\u5bf9\u78b3\u6b63\u79bb\u5b50\u7acb\u4f53\u9009\u62e9\u6027\uff1a\u5916\u6d88\u65cb\u4e09\u7ea7\u9187\u7684\u4e0d\u5bf9\u79f0\u8131\u6c27\u8fd8\u539f\u53cd\u5e94"},"content":{"rendered":"<p>\u672c\u6587\u4f5c\u8005\u00a0<strong>alberto-caeiro<\/strong><\/p>\n<p>\u745e\u58eb\u82cf\u9ece\u4e16\u8054\u90a6\u7406\u5de5(ETH Z\u00fcrich)\u7684<a href=\"\/\/www.gsbet888.com\/chemists\/2019\/04\/erick-m-carreira.html\">Erick M. Carreira<\/a>\u6700\u8fd1\u5728JACS\u4e0a\u62a5\u9053\u4e00\u79cd\u6d88\u65cb\u4e09\u7ea7\u9187\u7684\u4e0d\u5bf9\u79f0\u8131\u6c27\u8fd8\u539f\u53cd\u5e94\uff0c\u53cd\u5e94\u7ecf\u8fc7\u914d\u4f4d\u8bf1\u5bfc\u7684\u9633\u79bb\u5b50\u624b\u6027\u63a7\u5236\u8fc7\u7a0b\u3002<\/p>\n<p>&nbsp;<\/p>\n<blockquote><p><em>Coordination-Induced Stereocontrol over Carbocations: Asymmetric Reductive Deoxygenation of Racemic Tertiary Alcohols\u201d<\/em><\/p>\n<p>Mayuko Isomura, David A. Petrone, Erick M. Carreira,<\/p>\n<p><em>J. Am. Chem. Soc.,\u00a0<\/em><strong>2019<\/strong>, <em>141,<\/em> 4738.\u00a0<a href=\"https:\/\/pubs.acs.org.ccindex.cn\/doi\/10.1021\/jacs.9b00862\">DOI: 10.1021\/jacs.9b00862<\/a><\/p><\/blockquote>\n<p>&nbsp;<\/p>\n<h4><strong>\u80cc\u666f<\/strong><\/h4>\n<p>\u78b3\u6b63\u79bb\u5b50\u81ea\u88ab\u6b27\u62c9\u6559\u6388\u63d0\u51fa\u5e76\u88ab\u5e7f\u6cdb\u63a5\u53d7\u540e\uff0c\u5176\u5728\u5316\u5b66\u5408\u6210\u4e0a\u88ab\u5e7f\u6cdb\u5e94\u7528\uff0c\u7136\u800c\u5b83\u4eec\u5728\u4e0d\u5bf9\u79f0\u5408\u6210\u4e0a\u5374\u4e3e\u6b65\u7ef4\u8270\u3002\u78b3\u6b63\u79bb\u5b50\u7684<em>sp<sup>2<\/sup><\/em>\u6742\u5316\u5bfc\u81f4\u7684\u4e24\u4e2a\u524d\u624b\u6027\u9762\u5bf9\u5176\u4e0d\u5bf9\u79f0\u53cd\u5e94\u9020\u6210\u4e86\u6781\u5927\u7684\u969c\u788d<sup>[1]<\/sup>(\u56fe1A\u5de6)\u3002\u4e3a\u6b64\uff0c\u4e24\u79cd\u65b9\u6848\u88ab\u63d0\u51fa\u89e3\u51b3\u6b64\u95ee\u9898\u3002\u4e00\u79cd\u662f\u5e95\u7269\u624b\u6027\u63a7\u5236(\u56fe1A\u4e2d)\uff0c\u5728\u78b3\u6b63\u79bb\u5b50\u65c1\u5f15\u5165\u624b\u6027\u4e2d\u5fc3\uff0c\u53e6\u4e00\u79cd\u662f\u5f62\u6210\u624b\u6027\u79bb\u5b50\u5bf9(\u56fe1A\u53f3)\uff0c\u5f15\u5165\u624b\u6027\u6297\u8861\u79bb\u5b50\u63a7\u5236\u9009\u62e9\u6027\u3002\u8fd9\u4e9b\u65b9\u6cd5\u5728\u4e8c\u7ea7\u78b3\u6b63\u79bb\u5b50\u7684\u624b\u6027\u63a7\u5236\u53cd\u5e94\u4e2d\u88ab\u5e7f\u6cdb\u5e94\u7528\uff0c\u800c\u4e09\u7ea7\u78b3\u6b63\u79bb\u5b50\u7684\u53cd\u5e94\u4ecd\u9c9c\u6709\u62a5\u9053\u3002\u4f5c\u8005\u5728\u524d\u9762\u62a5\u9053\u8fc7\u8054\u70ef\u9187\u916f\u7684\u4e0d\u5bf9\u79f0\u70f7\u57fa\u53d6\u4ee3\u53cd\u5e94<sup>[2]<\/sup>(\u56fe1B\u53f3)\uff0c\u7406\u8bba\u7814\u7a76\u6307\u51fa\u53cd\u5e94\u4e2d\u5b58\u5728\u4e00\u79cd\u4eb2\u7535\u7684\u03b7<sup>2<\/sup>\u8054\u70ef\u914d\u4f53\u548c\u4e00\u4e2a\u9ad8\u5ea6\u79bb\u57df\u7684\u6b63\u7535\u8377\u3002\u8fd9\u4e0eS<sub>N<\/sub>1\u53cd\u5e94\u5f88\u76f8\u4f3c\uff0c\u56e0\u6b64\u4f5c\u8005\u5047\u8bbe\u8fd9\u4e00\u7279\u6027\u662f\u5426\u53ef\u4ee5\u7528\u6765\u5b9e\u73b0\u4e09\u7ea7\u78b3\u6b63\u79bb\u5b50\u7684\u4e0d\u5bf9\u79f0\u53cd\u5e94\u3002\u5728\u8fd9\u91cc\u624b\u6027\u4e2d\u5fc3\u662f\u5728\u4e0e\u5e95\u7269\u914d\u4f4d\u7684\u91d1\u5c5e\u4e0a\uff0c\u79bb\u5b50\u5316\u5f97\u5230\u7684\u78b3\u6b63\u79bb\u5b50\u56e0\u6b64\u6709\u4e86\u7a33\u5b9a\u7684\u624b\u6027\u73af\u5883(\u56fe1C)\u3002\u57281982\u5e74Siehl\u548cMayr\u7684\u5de5\u4f5c<sup>[3]<\/sup>\u4e2d\u8868\u660e\uff0c\u8fd9\u79cd\u8054\u70ef\u4e19\u57fa\u78b3\u6b63\u79bb\u5b50\u4f1a\u5728C<sub>\u03b1<\/sub>\u548cC<sub>\u03b3<\/sub>\u95f4\u79bb\u57df(\u56fe1D)\u3002\u56e0\u6b64\u5728\u8054\u70ef\u4e0e\u91d1\u5c5e\u914d\u4f4d\u540e\uff0c\u662f\u5426\u53d1\u751f\u78b3\u6b63\u79bb\u5b50\u7684\u79bb\u57df\u5bf9\u53cd\u5e94\u9009\u62e9\u6027\u6709\u5f88\u5927\u7684\u5f71\u54cd\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/ee6df7033a974fd2d6b73e2297a56fc1.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-25092\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/ee6df7033a974fd2d6b73e2297a56fc1.jpg\" alt=\"\" width=\"619\" height=\"829\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/ee6df7033a974fd2d6b73e2297a56fc1.jpg 619w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/ee6df7033a974fd2d6b73e2297a56fc1-224x300.jpg 224w\" sizes=\"(max-width: 619px) 100vw, 619px\" 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href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/4-2.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-25052 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/4-2.png\" alt=\"\" width=\"689\" height=\"617\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/4-2.png 689w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/4-2-300x269.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/4-2-680x609.png 680w\" sizes=\"(max-width: 689px) 100vw, 689px\" 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href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/5-2.png\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-25053 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/5-2.png\" alt=\"\" width=\"940\" height=\"604\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/5-2.png 940w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/5-2-300x193.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/5-2-768x493.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/5-2-680x437.png 680w\" sizes=\"(max-width: 940px) 100vw, 940px\" \/><\/a><\/p>\n<p>Bi(OTf)<sub>3<\/sub>\u662f\u4e00\u79cd\u6709\u673a\u6eb6\u5242\u4e2d\u6eb6\u89e3\u6027\u8f83\u5dee\u7684\u65e0\u673a\u76d0\uff0c\u800c\u8003\u8651\u5230\u4eb2\u6838\u8bd5\u5242\u8fdb\u653b\u5b8c\u5168\u7684\u8bdd\uff0c\u53cd\u5e94\u4f1a\u751f\u6210\u4e00\u5206\u5b50\u5e26\u6709Lewis\u9178\u6027\u7684\u5421\u5576OTf\uff0c\u6b64\u7269\u79cd\u4e5f\u4f1a\u4fc3\u8fdb\u5f62\u6210\u78b3\u6b63\u79bb\u5b50\u7684\u53cd\u5e94\uff0c\u56e0\u6b64\u4f5c\u8005\u505a\u4e86\u7cfb\u5217\u5bf9\u6bd4\u5b9e\u9a8c\u9a8c\u8bc1\u5176\u662f\u5426\u5177\u6709\u50ac\u5316\u6d3b\u6027\u3002\u5728\u65e0Bi(OTf)<sub>3<\/sub>\u5b58\u5728\u65f6\uff0c\u53cd\u5e94\u53ef\u6b63\u5e38\u8fdb\u884c\uff0c\u5f97\u5230\u53ef\u6bd4\u7684\u7ed3\u679c\u3002<\/p>\n<p>\u968f\u540e\u4f5c\u8005\u505a\u4e86\u7ebf\u6027\u81ea\u7531\u80fd\u5173\u7cfb\u56fe\uff0c\u5176\u62df\u5408\u65b9\u7a0b\u4e2d\uff0cHammett\u53d6\u4ee3\u5e38\u6570\u03c1=\u22121.15\uff0c\u8868\u660e\u51b3\u901f\u6b65\u4e2d\u751f\u6210\u4e86\u5927\u91cf\u7684\u6b63\u7535\u8377\uff0c\u8fd9\u4e0eS<em><sub>N<\/sub><\/em>1\u7684\u673a\u7406\u76f8\u543b\u5408\u3002<\/p>\n<p>\u4e3a\u4e86\u8fdb\u4e00\u6b65\u9a8c\u8bc1\u51b3\u901f\u6b65\uff0c\u4f5c\u8005\u505a\u4e86\u4e8c\u7ea7\u540c\u4f4d\u7d20\u5b9e\u9a8c\uff0c\u4e00\u822c\u6765\u8bf4\uff0c\u5f53\u4ece<em>sp<sup>3<\/sup><\/em>\u2192<em>sp<sup>2<\/sup><\/em>\u8f6c\u5316\u65f6\uff0c\u7531\u4e8e\u952e\u529b\u5e38\u6570\u7684\u53d8\u5316\uff0c\u540c\u4f4d\u7d20\u6548\u5e94K<em><sub>H<\/sub><\/em>\/K<em><sub>D<\/sub><\/em>\u4e3a1.2-1.1\uff0c\u800c\u6b64\u5904\u540c\u4f4d\u7d20\u6548\u5e94K<em><sub>H<\/sub><\/em>\/K<em><sub>D<\/sub><\/em>\u4e3a1.08\u00b10.01\uff0c\u867d\u7136\u4e0e\u6807\u51c6\u6570\u503c\u7565\u6709\u5dee\u5f02\uff0c\u4f46\u662f\u4ecd\u7136\u53ef\u4ee5\u8868\u660e\u51b3\u901f\u6b65\u4e2d\u5305\u542b<em>sp<sup>3<\/sup><\/em>\u2192<em>sp<sup>2<\/sup><\/em>\u7684\u8f6c\u5316\uff0c\u8fd9\u4e0eS<em><sub>N<\/sub><\/em>1\u53cd\u5e94\u76f8\u543b\u5408\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/6-2.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-25054 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/6-2.png\" alt=\"\" width=\"1001\" height=\"590\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/6-2.png 1001w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/6-2-300x177.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/6-2-768x453.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/6-2-680x401.png 680w\" sizes=\"(max-width: 1001px) 100vw, 1001px\" \/><\/a><\/p>\n<p>\u4f5c\u8005\u968f\u540e\u505a\u4e86\u90e8\u5206\u8f6c\u5316\u7684\u5b9e\u9a8c\uff0c\u6392\u9664\u4e86\u53ef\u80fd\u5b58\u5728\u7684\u52a8\u529b\u5b66\u62c6\u5206\u673a\u7406\u3002\u800c\u5bf9\u624b\u6027\u5e95\u7269\u7684\u53cd\u5e94\u8868\u660e\uff0c\u5e95\u7269\u7684\u624b\u6027\u662f\u7531\u50ac\u5316\u5242\u63a7\u5236\u7684\uff0c\u5e76\u4e14\u4e3a\u624b\u6027\u63a7\u5236\u63d0\u51fa\u4e00\u79cd\u53ef\u80fd\u7684\u6a21\u578b\u3002\u6700\u540e\uff0c\u4f5c\u8005\u6392\u9664\u4e86\u70ef\u4e19\u57fa\u9187\u7684\u53cd\u5e94\u53ef\u80fd\u6027\u3002<\/p>\n<p>\u4f5c\u8005\u901a\u8fc7\u4e0a\u8ff0\u673a\u7406\u7814\u7a76\u63a8\u6d4b\u5982\u4e0b\u673a\u7406\uff1a\u914d\u4f4d\u540e\u7684\u5e95\u7269\u5728Lewis\u9178\u50ac\u5316\u4e0b\u5f62\u6210\u78b3\u6b63\u79bb\u5b50\uff0c\u968f\u540e\u53d1\u751fC-C bondrotation\u540e\u53d1\u751f\u5bf9\u6620\u9009\u62e9\u6027\u7684\u4eb2\u6838\u8fdb\u653b\u5f97\u5230\u4ea7\u7269\uff0c\u6700\u540e\u5e95\u7269\u4ea7\u7269\u4ea4\u6362\u91cd\u542f\u50ac\u5316\u5faa\u73af\u5708\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/7-2.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-25055 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/7-2.png\" alt=\"\" width=\"996\" height=\"619\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/7-2.png 996w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/7-2-300x186.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/7-2-768x477.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/7-2-680x423.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2019\/04\/7-2-233x144.png 233w\" sizes=\"(max-width: 996px) 100vw, 996px\" \/><\/a><\/p>\n<h4><strong>\u53c2\u8003\u6587\u732e<\/strong><\/h4>\n<ol>\n<li>Naredla, R. R.; Klumpp, D. A., <em>Chem. Rev.,<\/em><strong>2013<\/strong>, <em>113,<\/em> 6905, <a href=\"https:\/\/pubs.acs.org.ccindex.cn\/doi\/10.1021\/cr4001385\">DOI: 10.1021\/cr4001385<\/a>;<\/li>\n<li>Petrone, D. A.; Isomura, M.; Franzoni, I.; R\u00f6ssler, S. L.; Carreira, E. M.,<em>J. Am. Chem. Soc.,<\/em><strong>2018<\/strong>, <em>140<\/em>, 4697, <a href=\"https:\/\/pubs.acs.org.ccindex.cn\/doi\/10.1021\/jacs.8b01416\">DOI: 10.1021\/jacs.8b01416<\/a>;<\/li>\n<li>a: Siehl, H.-U.; Mayr, H., <em>J. Am. Chem. Soc.,<\/em><strong>1982<\/strong>, <em>104<\/em>, 909, <a href=\"https:\/\/pubs.acs.org.ccindex.cn\/doi\/10.1021\/ja00367a069\">DOI: 10.1021\/ja00367a069<\/a>; b: For a review on stable carbocations, see: Olah, G. A.; Prakash Reddy, V.; Prakash, G. K. S., <em>Chem. Rev.,<\/em><strong>1992<\/strong>, <em>92<\/em>, 69, <a href=\"https:\/\/pubs.acs.org.ccindex.cn\/doi\/10.1021\/cr00009a003\">DOI: 10.1021\/cr00009a003<\/a>;<\/li>\n<li>Simmons, E. M.; Hartwig, J. F., <em>Angew. Chem., Int. Ed.,<\/em><strong>2012<\/strong>, <em>51<\/em>, 3066, <a href=\"https:\/\/onlinelibrary.wiley.com\/doi\/full\/10.1002\/anie.201107334\">DOI: 10.1002\/anie.201107334<\/a>;<\/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\u4f5c\u8005\u00a0alberto-caeiro \u745e\u58eb\u82cf\u9ece\u4e16\u8054\u90a6\u7406\u5de5(ETH Z\u00fcrich)\u7684Erick M. Carreira\u6700\u8fd1\u5728JACS\u4e0a\u62a5\u9053\u4e00\u79cd\u6d88\u65cb\u4e09\u7ea7\u9187\u7684\u4e0d\u5bf9\u79f0\u8131\u6c27\u8fd8\u539f\u53cd\u5e94\uff0c\u53cd\u5e94\u7ecf\u8fc7\u914d\u4f4d\u8bf1\u5bfc\u7684\u9633\u79bb\u5b50\u624b\u6027\u63a7\u5236\u8fc7\u7a0b\u3002 &nbsp; Coordination-Induced Stereocontrol over Carbocations: Asymmetric Reductive Deoxygenation of Racemic Tertiary Alcohols\u201d Mayuko Isomura, David A. Petrone, Erick M. Carreira, J. Am. Chem. Soc.,\u00a02019, 141, 4738.\u00a0DOI: 10.1021\/jacs.9b00862 &nbsp; \u80cc\u666f 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R.; Klumpp, D. A., Chem. Rev.,2013, 113, 6905, DOI: 10.1021\/cr4001385; Petrone, D. A.; Isomura, M.; Franzoni, I.; R\u00f6ssler, S. L.; Carreira, E. M.,J. Am. Chem. Soc.,2018, 140, 4697, DOI: 10.1021\/jacs.8b01416; a: Siehl, H.-U.; Mayr, H., J. Am. Chem. Soc.,1982, 104, 909, DOI: 10.1021\/ja00367a069; b: For a review on stable carbocations, see: Olah, G. 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