{"id":32861,"date":"2020-07-01T08:02:22","date_gmt":"2020-07-01T00:02:22","guid":{"rendered":"\/\/www.gsbet888.com\/?p=32861"},"modified":"2020-06-29T22:45:45","modified_gmt":"2020-06-29T14:45:45","slug":"%e7%82%94%e7%83%83%e3%80%81%e9%86%87%e5%92%8c%e4%b8%89%e4%bb%b7%e7%a2%98%e8%af%95%e5%89%82%e7%9a%84%e5%8c%ba%e5%9f%9f%e9%80%89%e6%8b%a9%e6%80%a7%e5%8f%8d%e5%bc%8f-12-%e5%8f%8c%e5%ae%98%e8%83%bd","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2020\/07\/%e7%82%94%e7%83%83%e3%80%81%e9%86%87%e5%92%8c%e4%b8%89%e4%bb%b7%e7%a2%98%e8%af%95%e5%89%82%e7%9a%84%e5%8c%ba%e5%9f%9f%e9%80%89%e6%8b%a9%e6%80%a7%e5%8f%8d%e5%bc%8f-12-%e5%8f%8c%e5%ae%98%e8%83%bd.html","title":{"rendered":"\u7094\u70c3\u3001\u9187\u548c\u4e09\u4ef7\u7898\u8bd5\u5242\u7684\u533a\u57df\u9009\u62e9\u6027\u53cd\u5f0f-1,2-\u53cc\u5b98\u80fd\u56e2\u5316\u53cd\u5e94"},"content":{"rendered":"<p>\u4e59\u70ef\u57fa\u919a\u662f\u4e00\u79cd\u91cd\u8981\u7684\u5bcc\u7535\u5b50\u70ef\u70c3\uff0c\u5e7f\u6cdb\u7528\u4e8e\u73af\u52a0\u6210\u548c\u514b\u83b1\u68ee\u91cd\u6392\u7b49C-C\u952e\u5f62\u6210\u53cd\u5e94\u3002\u4e59\u70ef\u57fa\u919a\u7684\u5408\u6210\u65b9\u6cd5\u5305\u62ec\u7094\u70c3\u7684\u6c22\u70f7\u6c27\u57fa\u5316\u53cd\u5e94\u3001\u70ef\u57fa\u5364\u5316\u7269\u6216\u70ef\u57fa\u787c\u9178\u916f\u4e0e\u9187\u7684C-C\u5076\u8054\u53cd\u5e94\u4ee5\u53ca\u70ef\u4e19\u57fa\u919a\u7684\u5f02\u6784\u5316\u53cd\u5e94\u7b49\uff0c\u4f46\u591a\u53d6\u4ee3\u4e59\u70ef\u57fa\u919a\u7684\u7acb\u4f53\u9009\u62e9\u6027\u5408\u6210\u4ecd\u7136\u9762\u4e34\u5de8\u5927\u6311\u6218<sup>[1]<\/sup>\uff08Scheme 1a\uff09\u3002\u6c22\u70f7\u6c27\u57fa\u5316\u53cd\u5e94\u5f88\u65e9\u5c31\u88ab\u5e94\u7528\u4e8e\u6709\u673a\u5316\u5408\u7269\u7684\u5408\u6210\u4e2d\uff0c\u4f46\u8be5\u7b56\u7565\u4e3b\u8981\u5c40\u9650\u4e8e\u672b\u7aef\u7094\u70c3\u3002\u7094\u57fa\u82ef\u7898\u916e\u88ab\u8bc1\u660e\u53ef\u4e0e\u915a\u53d1\u751f\u533a\u57df\u9009\u62e9\u6027\u52a0\u6210\u53cd\u5e94\u751f\u6210\u542b\u82ef\u7898\u916e\u7684\u4e59\u70ef\u57fa\u919a\uff0c\u4f46\u8be5\u53cd\u5e94\u9700\u8981\u5236\u5907\u590d\u6742\u7684\u7898\u8bd5\u5242\u4e14\u4e0d\u80fd\u5f97\u5230\u56db\u53d6\u4ee3\u884d\u751f\u7269<sup>[2]<\/sup>\uff08Scheme 1b\uff09\u3002\u4eb2\u7535\u5b50\u8bd5\u5242\uff08E<sup>+<\/sup>\uff09\u6d3b\u5316\u7684\u7094\u70c3\u4e0e\u9187\u53d1\u751f\u7acb\u4f53\u9009\u62e9\u6027\u52a0\u6210\u53cd\u5e94\u662f\u5408\u6210\u542b\u4eb2\u7535\u5b50\u8bd5\u5242\u4e59\u70ef\u57fa\u919a\u7684\u91cd\u8981\u65b9\u6cd5\u3002Yoshikai\u8bfe\u9898\u7ec4\u5f00\u53d1\u4e86\u542b\u4e09\u6c1f\u7532\u78fa\u9178\u6216\u6c1f\u7684\u4e09\u4ef7\u7898\u8bd5\u5242\u4e0e\u5185\u90e8\u7094\u70c3\u53d1\u751f\u53cd\u5f0f-\u53cc\u5b98\u80fd\u5316\u53cd\u5e94<sup>[3]<\/sup>\uff08Scheme 1c\uff09\uff0c\u5408\u6210\u7684\u4e09\u6c1f\u7532\u78fa\u9178\u4e59\u70ef\u916f\u53c8\u53ef\u8f6c\u5316\u4e3a\u91cd\u8981\u7684\u919a\u7c7b\u5316\u5408\u7269\u3002\u540c\u65f6\uff0cYoshikai\u8bfe\u9898\u7ec4\u5229\u7528Zhdankin\u8bfe\u9898\u7ec4\u5f00\u53d1\u7684\u4e09\u6c1f\u7532\u78fa\u9178\u53d6\u4ee3\u7684\u82ef\u7898\u916e\uff08BXT\uff09\u4f5c\u4e3aI(III)\u4eb2\u7535\u8bd5\u5242\u4fc3\u8fdb\u542b\u4eb2\u6838\u90e8\u5206\u7684\u7094\u70c3\u53d1\u751f\u201c\u7898(III)\u73af\u5316\u201d\u53cd\u5e94\uff0c\u751f\u6210\u542b\u82ef\u7898\u916e\u7684\u6742\u82b3\u70c3\u548c\u591a\u73af\u82b3\u70c3\u5316\u5408\u7269\u3002\u4e3a\u4e86\u5f00\u53d1\u51fa\u66f4\u4e3a\u6709\u6548\u7684\u5408\u6210\u4e59\u70ef\u57fa\u919a\u7684\u65b0\u65b9\u6cd5\uff0c\u65b0\u52a0\u5761\u5357\u6d0b\u7406\u5de5\u5927\u5b66<a href=\"https:\/\/www3.ntu.edu.sg\/home\/nyoshikai\/yoshikai_group\/members\/yoshikai.html\">Yoshikai\u8bfe\u9898\u7ec4<\/a> \uff08\u5316\u5b66\u7a7a\u95f4\uff1a<a href=\"\/\/www.gsbet888.com\/chemists\/%e4%b8%96%e7%95%8c%e9%9d%92%e5%b9%b4%e5%8c%96%e5%ad%a6%e5%ae%b6\/2020\/05\/%e5%90%89%e6%88%92-%e7%9b%b4%e5%bd%a6-naohiko-yoshikai.html\">Yoshikai\u4ecb\u7ecd<\/a>\uff09\u548c\u90d1\u5dde\u5927\u5b66<a href=\"http:\/\/www7.zzu.edu.cn\/rczp\/info\/1146\/1203.htm\">\u5434\u4fca\u826f\u8bfe\u9898\u7ec4<\/a>\u5171\u540c\u62a5\u9053\u4e86BXT\u3001\u9187\u548c\u7094\u70c3\u7684\u7acb\u4f53\u9009\u62e9\u6027\u53cd\u5f0f-1,2-\u53cc\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\uff0c\u80fd\u4ee5\u826f\u597d\u7684\u6536\u7387\u5f97\u5230\u591a\u53d6\u4ee3\u7684\u4e59\u70ef\u57fa\u919a\uff08Scheme 1d\uff09\u3002\u76f8\u5173\u7814\u7a76\u6210\u679c\u53d1\u8868\u4e8e<\/p>\n<blockquote><p>\u201cStereoselective Access to Highly Substituted Vinyl Ethers via trans-Difunctionalization of Alkynes with Alcohols and Iodine(III) Electrophile\u201d<\/p>\n<p>Ding, W.; Chai, J.; Wang, C.; Wu, J.;* Yoshikai, N.* <em>J. Am. Chem. Soc.<\/em> <strong>2020<\/strong>, Early View. DOI: <a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/jacs.0c04140\">10.1021\/jacs.0c04140<\/a><\/p><\/blockquote>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/1-86.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-32862 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/1-86.jpg\" alt=\"\" width=\"437\" height=\"619\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/1-86.jpg 437w, https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/1-86-212x300.jpg 212w\" sizes=\"(max-width: 437px) 100vw, 437px\" \/><\/a><\/p>\n<p style=\"text-align: center;\">Scheme 1 \u80cc\u666f\u7814\u7a76<\/p>\n<h4><strong>\u8bba\u6587\u6982\u8981<\/strong><\/h4>\n<p>\u5ba4\u6e29\u6761\u4ef6\u4e0b\uff0c1-\u82ef\u57fa-1-\u4e01\u7094<strong>2a<\/strong>\u548c<strong>1<\/strong>\u5728MeOH\u6eb6\u6db2\u4e2d\u53ef\u53d1\u751f\u53cd\u5f0f-1,2-\u53cc\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\uff0c\u80fd\u4ee598\uff05\u7684\u6536\u7387\u5f97\u5230\u03b2-\u03bb<sup>3<\/sup>-\u7898\u70f7\u57fa\u4e59\u70ef\u57fa\u919a<strong>4aa<\/strong>\uff08Scheme 2a\uff09\u3002\u4ee5\u82ef\u7532\u9187\u4e3a\u8bd5\u5242\uff0c\u53cc\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\u4e5f\u53ef\u4ee5\u53d1\u751f\u3002<strong>1<\/strong>\u3001<strong>2a<\/strong>\u548c\u82ef\u7532\u9187\u5728MeCN\u6eb6\u6db2\u4e2d\u53d1\u751f\u53cc\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\uff0c\u80fd\u4ee587\uff05\u7684\u6536\u7387\u5f97\u5230\u4ea7\u7269<strong>4ab<\/strong>\uff08Scheme 2b\uff09\u3002\u56e0\u6b64\uff0c\u4f5c\u8005\u5c06\u9187\u4f5c\u4e3a\u6eb6\u5242\u548c\u8bd5\u5242\u5206\u522b\u4f5c\u4e3a\u6761\u4ef6A\u548cB\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/2-84.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-32863 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/2-84.jpg\" alt=\"\" width=\"534\" height=\"399\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/2-84.jpg 534w, https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/2-84-300x224.jpg 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/2-84-265x197.jpg 265w\" sizes=\"(max-width: 534px) 100vw, 534px\" \/><\/a><\/p>\n<p style=\"text-align: center;\">Scheme 2 \u6761\u4ef6\u4f18\u5316<\/p>\n<p>\u5728\u6700\u4f18\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u8003\u5bdf\u4e86\u5185\u90e8\u7094\u70c3\u7684\u5e95\u7269\u8303\u56f4\uff08Scheme 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href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/3-70.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-32864 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/3-70.jpg\" alt=\"\" width=\"482\" height=\"625\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/3-70.jpg 482w, https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/3-70-231x300.jpg 231w\" sizes=\"(max-width: 482px) 100vw, 482px\" \/><\/a><\/p>\n<p style=\"text-align: center;\">Scheme 3 \u5e95\u7269\u6269\u5c55<\/p>\n<p>\u4e3a\u4e86\u8bc1\u660e\u53cd\u5e94\u7684\u5e94\u7528\u6f5c\u529b\uff0c\u4f5c\u8005\u53c8\u8fdb\u884c\u4e86\u4e00\u7cfb\u5217\u884d\u751f\u53cd\u5e94\uff08Scheme 4\uff09\u3002\u5728Pd\u50ac\u5316\u4f5c\u7528\u4e0b\uff0c<strong>4ba<\/strong>\u53ef\u53d1\u751fStille\u53cd\u5e94\u3001Sonogashira\u53cd\u5e94\u548cSuzuki-Miyaura\u5076\u8054\u53cd\u5e94\uff0c\u80fd\u4ee5\u826f\u597d\u7684\u6536\u7387\u5206\u522b\u5f97\u5230\u5404\u79cd\u5171\u8f6d\u4e59\u70ef\u57fa\u919a<strong>7<\/strong>\u3001<strong>8<\/strong>\u548c<strong>9<\/strong>\u3002\u5728\u4e0d\u540c\u6e29\u5ea6\u4e0b\uff0c<strong>4ba<\/strong>\u7684\u82ef\u7898\u916e\u90e8\u5206\u53ef\u9009\u62e9\u6027\u53d1\u751fRosenmund-von Braun\u6c30\u5316\u53cd\u5e94\u548c\u8fd8\u539f\u53cd\u5e94\uff0c\u80fd\u4ee5\u826f\u597d\u7684\u6536\u7387\u5206\u522b\u5f97\u5230\u03b2-\u6c30\u57fa\u4e59\u70ef\u57fa\u919a<strong>10<\/strong>\u548c\u03b2-\u7898\u4e59\u70ef\u57fa\u919a<strong>11<\/strong>\uff08Scheme 4a\uff09\u3002\u540c\u65f6\uff0c\u5728Pd\u50ac\u5316\u50ac\u5316\u4f5c\u7528\u4e0b\uff0c<strong>4ba<\/strong>\u7684BX\u90e8\u5206\u53d1\u751f\u52a0\u6c22\u8131\u5364\u53cd\u5e94\uff0c\u751f\u6210\u7684\u4ea7\u7269\u53ef\u53d1\u751fYb(OTf)<sub>3<\/sub>\u50ac\u5316\u7684Mannich\u53cd\u5e94\u3001\u4e0e\u539f\u4f4d\u751f\u6210\u76841,2-\u4e8c\u6c2e\u6742-1,3-\u4e8c\u70ef\u53d1\u751f\u9006\u7535\u5b50\u9700\u6c42\u5f97\u6c2e\u6742-DA\u53cd\u5e94\u4ee5\u53ca\u4e8c\u6c2f\u5361\u5bbe\u50ac\u5316\u7684\u73af\u4e19\u70f7\u5316\u53cd\u5e94\uff0c\u53ef\u4ee5\u826f\u597d\u7684\u6536\u7387\u5206\u522b\u5f97\u5230\u03b2-\u6c28\u57fa\u916e<strong>12<\/strong>\u3001\u56db\u6c22\u54d2\u55ea<strong>13<\/strong>\u548c\u73af\u4e19\u70f7<strong>14<\/strong>\uff08Scheme 4b\uff09\u3002\u03b2-\u7898\u57fa\u53d6\u4ee3\u7684\u70ef\u4e19\u57fa\u919a<strong>4am<\/strong>\u548c<strong>6am<\/strong>\u53ef\u53d1\u751f\u94dc\u8bf1\u5bfc\u7684\u8fd8\u539f\u53cd\u5e94\u548c\u514b\u83b1\u68ee\u91cd\u6392\u53cd\u5e94\u5206\u522b\u5f97\u5230\u03b1-\u7898\u70ef\u4e19\u57fa\u916e<strong>16a<\/strong>\u548c<strong>16b<\/strong>\uff08Scheme 4c\uff09\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/A-5.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-32867 \" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/A-5.jpg\" alt=\"\" width=\"578\" height=\"926\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/A-5.jpg 704w, https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/A-5-187x300.jpg 187w, https:\/\/assets.www.gsbet888.com\/uploads\/2020\/05\/A-5-639x1024.jpg 639w\" sizes=\"(max-width: 578px) 100vw, 578px\" \/><\/a><\/p>\n<p style=\"text-align: center;\">Scheme 4 \u884d\u751f\u53cd\u5e94<\/p>\n<h4><strong>\u8bba\u6587\u603b\u7ed3\u8bc4\u4ef7<\/strong><\/h4>\n<p>\u65b0\u52a0\u5761\u5357\u6d0b\u7406\u5de5\u5927\u5b66Yoshikai\u8bfe\u9898\u7ec4\u548c\u90d1\u5dde\u5927\u5b66\u5434\u4fca\u826f\u8bfe\u9898\u7ec4\u5171\u540c\u62a5\u9053\u4e86BXT\u3001\u9187\u548c\u7094\u70c3\u7684\u7acb\u4f53\u9009\u62e9\u6027\u53cd\u5f0f-1,2-\u53cc\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\u3002\u5404\u79cd\u672b\u7aef\u7094\u70c3\u3001\u5185\u90e8\u7094\u70c3\u4ee5\u53ca\u5404\u79cd\u9187\u5747\u80fd\u9002\u5e94\u53cd\u5e94\u6761\u4ef6\uff0c\u80fd\u4ee5\u826f\u597d\u7684\u6536\u7387\u548c\u4f18\u79c0\u7684\u533a\u57df\u9009\u62e9\u6027\u5f97\u5230\u4e00\u7cfb\u5217\u7a33\u5b9a\u7684\u53cd\u5f0f-\u03b2-\u7898\u4e59\u70ef\u57fa\u919a\u3002\u5176\u4e2d\uff0c\u4ea7\u7269\u7684\u82ef\u7898\u916e\u90e8\u5206\u80fd\u53d1\u751f\u5404\u79cd\u884d\u751f\u53cd\u5e94\uff0c\u8f6c\u5316\u4e3a\u591a\u53d6\u4ee3\u4e59\u70ef\u57fa\u919a\u3002<\/p>\n<h4><strong>\u53c2\u8003\u6587\u732e<\/strong><\/h4>\n<ul>\n<li>[1] Earnshaw, C.; Wallis, C. J.; Warren, S<em>. J. Chem. Soc., Perkin Trans. 1 <\/em><strong>1979<\/strong>, 3099-3106. DOI: <a href=\"https:\/\/pubs.rsc.org\/en\/results?artrefjournalname=j.%20chem.%20soc.,%20perkin%20trans.%201&amp;artrefstartpage=3106&amp;artrefvolumeyear=1979&amp;fcategory=journal\">10.1039\/P19790003099<\/a><\/li>\n<li>[2] Liu, B.; Lim, C. H.; Miyake, G. M. <em>J. Am. Chem. Soc<\/em>. <strong>2018<\/strong>, <em>140<\/em>, 12829-12835. DOI: <a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/jacs.8b05870\">10.1021\/jacs.8b05870<\/a><\/li>\n<li>[3] (a) Ochiai, M.; Hirobe, M.; Yoshimura, A.; Nishi, Y.; Miyamoto, K.; Shiro, M. <em>Org. Lett.. <\/em><strong>2007<\/strong>, <em>9<\/em>, 3335-3338. DOI: <a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ol071345q\">10.1021\/ol071345q<\/a> (b) Zhdankin, V. V.; Kuehl, C. J.; Krasutsky, A. P.; Bolz, J. T.; Simonsen, A. J. <em>J. Org. Chem.<\/em> <strong>1996<\/strong>, <em>61<\/em>, 6547-6551. DOI: <a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/jo960927a\">10.1021\/jo960927a<\/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":"\u4e59\u70ef\u57fa\u919a\u662f\u4e00\u79cd\u91cd\u8981\u7684\u5bcc\u7535\u5b50\u70ef\u70c3\uff0c\u5e7f\u6cdb\u7528\u4e8e\u73af\u52a0\u6210\u548c\u514b\u83b1\u68ee\u91cd\u6392\u7b49C-C\u952e\u5f62\u6210\u53cd\u5e94\u3002\u4e59\u70ef\u57fa\u919a\u7684\u5408\u6210\u65b9\u6cd5\u5305\u62ec\u7094\u70c3\u7684\u6c22\u70f7\u6c27\u57fa\u5316\u53cd\u5e94\u3001\u70ef\u57fa\u5364\u5316\u7269\u6216\u70ef\u57fa\u787c\u9178\u916f\u4e0e\u9187\u7684C-C\u5076\u8054\u53cd\u5e94\u4ee5\u53ca\u70ef\u4e19\u57fa\u919a\u7684\u5f02\u6784\u5316\u53cd\u5e94\u7b49\uff0c\u4f46\u591a\u53d6\u4ee3\u4e59\u70ef\u57fa\u919a\u7684\u7acb\u4f53\u9009\u62e9\u6027\u5408\u6210\u4ecd\u7136\u9762\u4e34\u5de8\u5927\u6311\u6218[1]\uff08Scheme 1a\uff09\u3002\u6c22\u70f7\u6c27\u57fa\u5316\u53cd\u5e94\u5f88\u65e9\u5c31\u88ab\u5e94\u7528\u4e8e\u6709\u673a\u5316\u5408\u7269\u7684\u5408\u6210\u4e2d\uff0c\u4f46\u8be5\u7b56\u7565\u4e3b\u8981\u5c40\u9650\u4e8e\u672b\u7aef\u7094\u70c3\u3002\u7094\u57fa\u82ef\u7898\u916e\u88ab\u8bc1\u660e\u53ef\u4e0e\u915a\u53d1\u751f\u533a\u57df\u9009\u62e9\u6027\u52a0\u6210\u53cd\u5e94\u751f\u6210\u542b\u82ef\u7898\u916e\u7684\u4e59\u70ef\u57fa\u919a\uff0c\u4f46\u8be5\u53cd\u5e94\u9700\u8981\u5236\u5907\u590d\u6742\u7684\u7898\u8bd5\u5242\u4e14\u4e0d\u80fd\u5f97\u5230\u56db\u53d6\u4ee3\u884d\u751f\u7269[2]\uff08Scheme 1b\uff09\u3002\u4eb2\u7535\u5b50\u8bd5\u5242\uff08E+\uff09\u6d3b\u5316\u7684\u7094\u70c3\u4e0e\u9187\u53d1\u751f\u7acb\u4f53\u9009\u62e9\u6027\u52a0\u6210\u53cd\u5e94\u662f\u5408\u6210\u542b\u4eb2\u7535\u5b50\u8bd5\u5242\u4e59\u70ef\u57fa\u919a\u7684\u91cd\u8981\u65b9\u6cd5\u3002Yoshikai\u8bfe\u9898\u7ec4\u5f00\u53d1\u4e86\u542b\u4e09\u6c1f\u7532\u78fa\u9178\u6216\u6c1f\u7684\u4e09\u4ef7\u7898\u8bd5\u5242\u4e0e\u5185\u90e8\u7094\u70c3\u53d1\u751f\u53cd\u5f0f-\u53cc\u5b98\u80fd\u5316\u53cd\u5e94[3]\uff08Scheme 1c\uff09\uff0c\u5408\u6210\u7684\u4e09\u6c1f\u7532\u78fa\u9178\u4e59\u70ef\u916f\u53c8\u53ef\u8f6c\u5316\u4e3a\u91cd\u8981\u7684\u919a\u7c7b\u5316\u5408\u7269\u3002\u540c\u65f6\uff0cYoshikai\u8bfe\u9898\u7ec4\u5229\u7528Zhdankin\u8bfe\u9898\u7ec4\u5f00\u53d1\u7684\u4e09\u6c1f\u7532\u78fa\u9178\u53d6\u4ee3\u7684\u82ef\u7898\u916e\uff08BXT\uff09\u4f5c\u4e3aI(III)\u4eb2\u7535\u8bd5\u5242\u4fc3\u8fdb\u542b\u4eb2\u6838\u90e8\u5206\u7684\u7094\u70c3\u53d1\u751f\u201c\u7898(III)\u73af\u5316\u201d\u53cd\u5e94\uff0c\u751f\u6210\u542b\u82ef\u7898\u916e\u7684\u6742\u82b3\u70c3\u548c\u591a\u73af\u82b3\u70c3\u5316\u5408\u7269\u3002\u4e3a\u4e86\u5f00\u53d1\u51fa\u66f4\u4e3a\u6709\u6548\u7684\u5408\u6210\u4e59\u70ef\u57fa\u919a\u7684\u65b0\u65b9\u6cd5\uff0c\u65b0\u52a0\u5761\u5357\u6d0b\u7406\u5de5\u5927\u5b66Yoshikai\u8bfe\u9898\u7ec4 \uff08\u5316\u5b66\u7a7a\u95f4\uff1aYoshikai\u4ecb\u7ecd\uff09\u548c\u90d1\u5dde\u5927\u5b66\u5434\u4fca\u826f\u8bfe\u9898\u7ec4\u5171\u540c\u62a5\u9053\u4e86BXT\u3001\u9187\u548c\u7094\u70c3\u7684\u7acb\u4f53\u9009\u62e9\u6027\u53cd\u5f0f-1,2-\u53cc\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\uff0c\u80fd\u4ee5\u826f\u597d\u7684\u6536\u7387\u5f97\u5230\u591a\u53d6\u4ee3\u7684\u4e59\u70ef\u57fa\u919a\uff08Scheme 1d\uff09\u3002\u76f8\u5173\u7814\u7a76\u6210\u679c\u53d1\u8868\u4e8e \u201cStereoselective Access to Highly Substituted Vinyl Ethers via trans-Difunctionalization of Alkynes with Alcohols and Iodine(III) Electrophile\u201d Ding, W.; Chai, J.; Wang, C.; Wu, J.;* Yoshikai, N.* J. Am. Chem. Soc. 2020, Early View. DOI: 10.1021\/jacs.0c04140 Scheme 1 \u80cc\u666f\u7814\u7a76 \u8bba\u6587\u6982\u8981 \u5ba4\u6e29\u6761\u4ef6\u4e0b\uff0c1-\u82ef\u57fa-1-\u4e01\u70942a\u548c1\u5728MeOH\u6eb6\u6db2\u4e2d\u53ef\u53d1\u751f\u53cd\u5f0f-1,2-\u53cc\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\uff0c\u80fd\u4ee598\uff05\u7684\u6536\u7387\u5f97\u5230\u03b2-\u03bb3-\u7898\u70f7\u57fa\u4e59\u70ef\u57fa\u919a4aa\uff08Scheme 2a\uff09\u3002\u4ee5\u82ef\u7532\u9187\u4e3a\u8bd5\u5242\uff0c\u53cc\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\u4e5f\u53ef\u4ee5\u53d1\u751f\u30021\u30012a\u548c\u82ef\u7532\u9187\u5728MeCN\u6eb6\u6db2\u4e2d\u53d1\u751f\u53cc\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\uff0c\u80fd\u4ee587\uff05\u7684\u6536\u7387\u5f97\u5230\u4ea7\u72694ab\uff08Scheme 2b\uff09\u3002\u56e0\u6b64\uff0c\u4f5c\u8005\u5c06\u9187\u4f5c\u4e3a\u6eb6\u5242\u548c\u8bd5\u5242\u5206\u522b\u4f5c\u4e3a\u6761\u4ef6A\u548cB\u3002 Scheme 2 \u6761\u4ef6\u4f18\u5316 \u5728\u6700\u4f18\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u8003\u5bdf\u4e86\u5185\u90e8\u7094\u70c3\u7684\u5e95\u7269\u8303\u56f4\uff08Scheme 3\uff09\u3002R1\u53d6\u4ee3\u57fa\u4e3a\u5404\u79cd\u82b3\u57fa\u6216\u8102\u80aa\u65cf\u3001R2\u53d6\u4ee3\u57fa\u4e3a\u5404\u79cd\u4eb2\u7535\u3001\u4eb2\u6838\u82b3\u57fa\u53d6\u4ee3\u6216\u6742\u73af\u82b3\u57fa\u53d6\u4ee3\u7684\u5185\u90e8\u7094\u70c3\u5747\u80fd\u8f83\u597d\u7684\u9002\u5e94\u53cd\u5e94\u6761\u4ef6\uff0c\u80fd\u4ee5\u826f\u597d\u81f3\u4f18\u79c0\u7684\u6536\u7387\u548c\u4f18\u79c0\u7684\u533a\u57df\u9009\u62e9\u6027\u5f97\u5230\u76f8\u5e94\u4ea7\u7269\u3002\u4f46\u7532\u57fa\u6216\u4f2f\u70f7\u57fa\u53d6\u4ee3\u7684\u5185\u90e8\u7094\u70c3\u53ea\u80fd\u4ee5\u9002\u5f53\u7684\u533a\u57df\u9009\u62e9\u6027\u5f97\u5230\u76f8\u5e94\u4ea7\u7269\u3002\u63a5\u7740\uff0c\u4f5c\u8005\u8003\u5bdf\u4e86\u9187\u7684\u5e95\u7269\u8303\u56f4\u3002\u5404\u79cd\u4f2f\u9187\u3001\u4ef2\u9187\u3001\u542b\u7f9f\u57fa\u3001\u6c30\u57fa\u3001\u7532\u7845\u70f7\u57fa\u3001\u70ef\u4e19\u57fa\u7b49\u529f\u80fd\u6027\u57fa\u56e2\u7684\u9187\u4ee5\u53ca(-)-\u8584\u8377\u9187\u548c\u96c4\u753e\u916e\u5747\u80fd\u8f83\u597d\u7684\u9002\u5e94\u53cd\u5e94\u6761\u4ef6\uff0c\u80fd\u4ee5\u4e2d\u7b49\u81f3\u4f18\u79c0\u7684\u7684\u6536\u7387\u5f97\u5230\u76f8\u5e94\u4ea7\u7269\uff0c\u4f46\u53d4\u9187\u4e0d\u80fd\u9002\u5e94\u53cd\u5e94\u6761\u4ef6\u3002\u82e5\u5c06\u8102\u80aa\u9187\u6362\u6210\u915a\u3001\u7fa7\u9170\u80fa\u3001\u78fa\u9170\u80fa\u548c\u786b\u9187\u7b49\u4eb2\u6838\u8bd5\u5242\uff0c\u53cc\u5b98\u80fd\u56e2\u5316\u4e5f\u4e0d\u80fd\u6b63\u5e38\u53cd\u5e94\u3002 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\u884d\u751f\u53cd\u5e94 \u8bba\u6587\u603b\u7ed3\u8bc4\u4ef7 \u65b0\u52a0\u5761\u5357\u6d0b\u7406\u5de5\u5927\u5b66Yoshikai\u8bfe\u9898\u7ec4\u548c\u90d1\u5dde\u5927\u5b66\u5434\u4fca\u826f\u8bfe\u9898\u7ec4\u5171\u540c\u62a5\u9053\u4e86BXT\u3001\u9187\u548c\u7094\u70c3\u7684\u7acb\u4f53\u9009\u62e9\u6027\u53cd\u5f0f-1,2-\u53cc\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\u3002\u5404\u79cd\u672b\u7aef\u7094\u70c3\u3001\u5185\u90e8\u7094\u70c3\u4ee5\u53ca\u5404\u79cd\u9187\u5747\u80fd\u9002\u5e94\u53cd\u5e94\u6761\u4ef6\uff0c\u80fd\u4ee5\u826f\u597d\u7684\u6536\u7387\u548c\u4f18\u79c0\u7684\u533a\u57df\u9009\u62e9\u6027\u5f97\u5230\u4e00\u7cfb\u5217\u7a33\u5b9a\u7684\u53cd\u5f0f-\u03b2-\u7898\u4e59\u70ef\u57fa\u919a\u3002\u5176\u4e2d\uff0c\u4ea7\u7269\u7684\u82ef\u7898\u916e\u90e8\u5206\u80fd\u53d1\u751f\u5404\u79cd\u884d\u751f\u53cd\u5e94\uff0c\u8f6c\u5316\u4e3a\u591a\u53d6\u4ee3\u4e59\u70ef\u57fa\u919a\u3002 \u53c2\u8003\u6587\u732e [1] Earnshaw, C.; Wallis, C. J.; Warren, S. J. Chem. Soc., Perkin Trans. 1 1979, 3099-3106. DOI: 10.1039\/P19790003099 [2] Liu, B.; Lim, C. H.; Miyake, G. M. J. Am. Chem. Soc. 2018, 140, 12829-12835. 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