{"id":25427,"date":"2019-05-28T10:21:21","date_gmt":"2019-05-28T02:21:21","guid":{"rendered":"\/\/www.gsbet888.com\/?p=25427"},"modified":"2019-05-28T10:21:21","modified_gmt":"2019-05-28T02:21:21","slug":"barton-zard%e5%8f%8d%e5%ba%94%e4%b8%ad%e9%97%b4%e4%bd%93%e7%9a%84%e5%8a%a8%e5%8a%9b%e5%ad%a6%e6%8b%86%e5%88%86","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2019\/05\/barton-zard%e5%8f%8d%e5%ba%94%e4%b8%ad%e9%97%b4%e4%bd%93%e7%9a%84%e5%8a%a8%e5%8a%9b%e5%ad%a6%e6%8b%86%e5%88%86.html","title":{"rendered":"Barton-Zard\u53cd\u5e94\u4e2d\u95f4\u4f53\u7684\u52a8\u529b\u5b66\u62c6\u5206"},"content":{"rendered":"
\u8f74\u624b\u6027\u5316\u5408\u7269\u5e7f\u6cdb\u5b58\u5728\u4e8e\u5929\u7136\u4ea7\u7269\u3001\u836f\u7269\u3001\u914d\u4f53\u53ca\u50ac\u5316\u5242\u4e2d\uff0c\u56e0\u6b64\u5408\u6210\u624b\u6027\u8054\u82b3\u57fa\u5316\u5408\u7269\u4e00\u76f4\u662f\u5316\u5b66\u5bb6\u5173\u6ce8\u7684\u91cd\u4e2d\u4e4b\u91cd\u3002\u5408\u6210\u8f74\u624b\u6027\u5316\u5408\u7269\u7684\u65b9\u6cd5\u4e3b\u8981\u67094\u79cd\uff1aa\uff09\u4e24\u4e2a\u82b3\u57fa\u5355\u4f4d\u53d1\u751f\u4e0d\u5bf9\u79f0\u5076\u8054\u53cd\u5e94; b\uff09\u5df2\u5b58\u5728\u7684\u8054\u82b3\u57fa\u5316\u5408\u7269\u53bb\u5bf9\u79f0\u5316\uff1bc\uff09\u53d6\u4ee3\u82b3\u57fa\u5316\u5408\u7269\u7684\u963b\u8f6c\u9009\u62e9\u6027; d\uff09\u8054\u82b3\u57fa\u5316\u5408\u7269\u7684\u52a8\u529b\u5b66\u62c6\u5206\u3002Scheme 1a\u5219\u662f\u6b64\u524d\u62a5\u9053\u7684\u53d6\u4ee3\u82b3\u57fa\u5316\u5408\u7269\u7684\u4e0d\u5bf9\u79f0\u52a0\u6210\u4ea7\u7269\u53d1\u751f\u624b\u6027\u4e2d\u5fc3\u5411\u8f74\u624b\u6027\u7684\u4f20\u9012\u8fc7\u7a0b\uff0c\u5f97\u5230\u542b\u4e94\u5143\u6742\u73af\u7684\u8f74\u624b\u6027\u5316\u5408\u7269\u3002\u8fd9\u79cd\u5408\u6210\u8f74\u624b\u6027\u7684\u65b9\u6cd5\u5f88\u65e9\u5c31\u88ab\u63d0\u51fa\uff0c\u4e14\u53d6\u5f97\u4e86\u4e0d\u9519\u7684\u8fdb\u5c55\uff0c\u4f46\u5173\u4e8e\u901a\u8fc7\u81ea\u8eab\u8f6c\u5316\u6784\u5efa\u542b\u4e94\u5143\u6742\u73af\u7684\u8f74\u624b\u6027\u9aa8\u67b6\u7684\u62a5\u9053\u8fd8\u6bd4\u8f83\u5c11\u3002\u53e6\u4e00\u65b9\u9762\uff0c\u5916\u6d88\u65cb\u4e8c\u82b3\u57fa\u5316\u5408\u7269\u7684\u52a8\u529b\u5b66\u62c6\u5206\u53ef\u901a\u8fc7\u9187\u89e3\u3001N-\u9170\u5316\/\u70f7\u57fa\u5316\u3001O-\u9170\u5316\u4ee5\u53ca\u76f4\u63a5\u82b3\u57fa\u5b98\u80fd\u56e2\u5316\u5b9e\u73b0\uff0c\u4f46\u5230\u76ee\u524d\u4e3a\u6b62\uff0c\u8fd8\u6ca1\u6709\u5173\u4e8e\u5916\u6d88\u65cb\u975e\u4e8c\u82b3\u57fa\u5316\u5408\u7269\u7684\u52a8\u529b\u5b66\u62c6\u5206\u7684\u62a5\u9053\u3002\u6700\u8fd1\uff0c\u745e\u58eb\u6d1b\u6851\u8054\u90a6\u7406\u5de5\u5927\u5b66\u795d\u4ecb\u5e73\u8bfe\u9898\u7ec4<\/a>\u62a5\u9053\u4e86\u5f02\u6c30\u4e59\u9178\u916f\u548c\u7094\u57fa\u916e\u7684\u4e0d\u5bf9\u79f0\u6742\u73af\u53cd\u5e94\uff0c\u6784\u5efa\u8f74\u624b\u6027\u82b3\u57fa\u5421\u54af\u9aa8\u67b6[1]\u3002\u5728\u6b64\u57fa\u7840\u4e0a\uff0c\u4f5c\u8005\u60f3\u8981\u5c06\u52a8\u529b\u5b66\u62c6\u5206\u5f15\u5165\u8f74\u624b\u6027\u82b3\u57fa\u5421\u54af\u5316\u5408\u7269\u7684\u5408\u6210\u4e2d\uff0c\u5373\u5b98\u80fd\u56e2\u53d6\u4ee3\u7684\u82b3\u73af\u53d1\u751f\u73af\u5316\u53cd\u5e94\u53ef\u5f97\u5230\u6d88\u65cb\u7684\u4ea7\u72692<\/strong>\u3002\u5728\u5408\u9002\u7684\u50ac\u5316\u5242\u4f5c\u7528\u4e0b\uff0c2<\/strong>\u53ef\u53d1\u751f\u6c27\u5316\u53cd\u5e94\u6216\u6d88\u9664\u53cd\u5e94\u4ece\u800c\u5b9e\u73b02<\/strong>\u7684\u52a8\u529b\u5b66\u62c6\u5206\u8fc7\u7a0b\uff0c\u5f97\u5230\u8f74\u624b\u6027\u5316\u5408\u72693<\/strong>\u3002\u540c\u65f6\uff0c\u56de\u6536\u76842<\/strong>\u53ef\u8f6c\u5316\u4e3a\u53cd\u6784\u578b\u7684\u4ea7\u72693<\/strong>\uff08Scheme 1b\uff09\u30023,4-\u4e8c\u6c22-2H<\/em>-\u5421\u54af6<\/strong>\u4e3aBarton-Zard\u53cd\u5e94\u7684\u4e2d\u95f4\u4f53\uff0c\u4f5c\u8005\u63a8\u6d4b6\u53ef\u6210\u529f\u5b9e\u73b0\u52a8\u529b\u5b66\u62c6\u5206\u8fc7\u7a0b\u3002\u56e0\u6b64\uff0c\u795d\u4ecb\u5e73\u8bfe\u9898\u7ec4<\/a>\u6210\u529f\u5f00\u53d1\u4e86\u78b1\u6027\u50ac\u5316\u4f5c\u7528\u4e0b\u785d\u57fa\u70ef\u70c34<\/strong>\u4e0e\u03b1-\u5f02\u6c30\u57fa\u4e59\u9178\u916f5<\/strong>\u53d1\u751f\u73af\u5316\u53cd\u5e94\u751f\u6210\u6d88\u65cb\u4ea7\u72696<\/strong>\u3002\u5728\u594e\u5b81\u884d\u751f\u7684\u786b\u8132\u50ac\u5316\u5242\u4f5c\u7528\u4e0b\uff0c\u4f5c\u8005\u6210\u529f\u5b9e\u73b0\u4e866<\/strong>\u7684\u52a8\u529b\u5b66\u62c6\u5206\uff0c\u5408\u6210\u8f74\u624b\u6027\u82b3\u57fa\u5316\u5408\u7269\uff08Scheme 1c\uff09\u3002<\/p>\n Catalytic Kinetic Resolution via Enantioselective Aromatization: Conversion of Racemic Intermediates of the Barton-Zard Reaction to Enantioenriched 3-Arylpyrroles<\/p>\n Zheng, S.-C.; Wang, Q.; Zhu, J.* Angew. Chem. Int. Ed. <\/em>2019, Just Accepted Manuscript<\/p>\n DOI: 10.1002\/anie.201903589<\/p><\/blockquote>\n \u8bba\u6587<\/strong>\u4f5c\u8005<\/strong>\uff1a\u795d\u4ecb\u5e73\u6559\u6388<\/p>\n <\/p>\n <\/p>\n <\/p>\n \u4e3b\u8981\u4ece\u4e8b\u590d\u6742\u5929\u7136\u4ea7\u7269\u5168\u5408\u6210\u3001\u4e0d\u5bf9\u79f0\u50ac\u5316\u4e0e\u5408\u6210\u548c\u591a\u7ec4\u5206\u4e32\u8054\u53cd\u5e94\u9886\u57df\u7684\u7814\u7a76\u3002<\/p>\n <\/p>\n \u6587\u732e\u8c03\u7814\u663e\u793a\u5df2\u6709\u5173\u4e8e\u785d\u57fa\u70ef\u70c34<\/strong>\u4e0e\u03b1-\u5f02\u6c30\u57fa\u4e59\u9178\u916f5<\/strong>\u53d1\u751f[3+2]\u73af\u52a0\u6210\u53cd\u5e94\u5408\u62102,3-\u4e8c\u6c22\u5421\u54af\u7684\u62a5\u9053\uff0c\u4f46\u7531\u4e8e\u5728DBU\u6216\u80cd\u50ac\u5316\u4f5c\u7528\u4e0b\uff0c\u4ea7\u7269\u4f1a\u8fc5\u901f\u8131\u6389HNO2<\/sub>\uff0c\u6240\u4ee5\u672a\u5206\u79bb\u51fa\u4e2d\u95f4\u4f536<\/strong>\u3002\u56e0\u6b64\uff0c\u4e3a\u5206\u79bb\u51fa\u4e2d\u95f4\u4f536a<\/strong>\uff0c\u4f5c\u8005\u4ee54a<\/strong>\u548c5a<\/strong>\u4e3a\u6a21\u677f\u5e95\u7269\uff0c\u5bf9\u53cd\u5e94\u6761\u4ef6\u8fdb\u884c\u53cd\u590d\u7b5b\u9009\uff0c\u786e\u5b9a\u6700\u4f73\u6761\u4ef6\u4e3a(Table 1)\uff1a1.0 equiv KHMDS\uff080.5 N\u5728\u7532\u82ef\u4e2d\uff09\u4e3a\u6700\u4f18\u78b1\uff0cDCE\u4e3a\u6700\u4f18\u6eb6\u5242\uff0c\u5728-25 \u00b0C\u6761\u4ef6\u4e0b\u53cd\u5e9448 h\uff0c\u80fd\u4ee567\uff05\u7684\u6536\u7387\u5f97\u5230\u4e2d\u95f4\u4f536a<\/strong>\u3002<\/p>\n <\/p>\n \u7d27\u63a5\u7740\uff0c\u4f5c\u8005\u5bf9(\u00b1)-6a<\/strong>\u7684\u52a8\u529b\u5b66\u62c6\u5206\u6761\u4ef6\u8fdb\u884c\u4f18\u5316\uff0c\u53d1\u73b00.1 equiv\u594e\u5b81\u884d\u751f\u7269\u786b\u8132A\u4e3a\u50ac\u5316\u5242\uff0c1.2 equiv K3<\/sub>PO4<\/sub>\u4e3a\u78b1\uff0c100 mg 5\u00c5\u5206\u5b50\u7b5b\u4e3a\u6dfb\u52a0\u7269\uff0c\u5728\u5ba4\u6e29\u6761\u4ef6\u4e0b\u53cd\u5e9448 h\uff0c\u80fd\u4ee551%\u7684\u6536\u7387\u548c86%\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230\u76f8\u5e94\u4ea7\u7269(+)-7a<\/strong>\uff1b\u540c\u65f6\uff0c\u53ef\u4ee549%\u7684\u6536\u7387\u548c88%\u7684\u5bf9\u6620\u9009\u62e9\u6027\u56de\u6536(+)-6a<\/strong>(Table 2) \u3002<\/p>\n \u5728\u6700\u4f18\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u5bf9\u8be5\u52a8\u529b\u5b66\u62c6\u5206\u7684\u5e95\u7269\u8303\u56f4\u8fdb\u884c\u8003\u5bdf\uff08Scheme 2\uff09\u3002\u5404\u79cd\u8418\u57fa\u53d6\u4ee3\u3001C-4\u4f4d\u7532\u57fa\u3001\u4e59\u57fa\u3001\u5f02\u4e19\u57fa\u3001\u82c4\u57fa\u53d6\u4ee3\u3001C-2\u4f4d\u7532\u6c27\u57fa\u7fb0\u57fa\u3001\u4e59\u6c27\u57fa\u7fb0\u57fa\u53d6\u4ee3\u5421\u54af\u30013-\uff082′-\u7532\u6c27\u57fa-6′-\u7532\u57fa\u82ef\u57fa\uff09\u5421\u54af\u5747\u80fd\u8f83\u597d\u7684\u9002\u5e94\u53cd\u5e94\u6761\u4ef6\uff0c\u80fd\u4ee5\u8f83\u9ad8\u7684\u6536\u7387\u548c\u5bf9\u6620\u9009\u62e9\u6027\u5f97\u5230\u76f8\u5e94\u4ea7\u7269\u3002\u800cC-2\u4f4d\u53d4\u4e01\u6c27\u57fa\u7fb0\u57fa\u548c\u82c4\u6c27\u57fa\u7fb0\u57fa\u53d6\u4ee3\u7684\u5421\u54af\u7684\u5bf9\u6620\u9009\u62e9\u6027\u7565\u5fae\u6709\u6240\u964d\u4f4e\u3002\u5e26\u4e24\u4e2a5\u5143\u6742\u73af\u7684\u5421\u54af\u4ee5\u53ca\uff08\u00b1\uff09-3,4-\u4e8c\u6c22-2H-\u5421\u54af\u4e5f\u80fd\u9002\u5e94\u53cd\u5e94\u6761\u4ef6\uff0c\u4f46\u5176\u6536\u7387\u8f83\u4f4e\u3002<\/p>\n \u4ee5\u594e\u5c3c\u4e01\u884d\u751f\u7684\u786b\u8132B\u4e3a\u50ac\u5316\u5242\uff0c5\u00c5\u5206\u5b50\u7b5b\u4e3a\u6dfb\u52a0\u7269\uff0c\u7532\u82ef\u4e3a\u6eb6\u5242\uff0c 30\u00b0C\u6761\u4ef6\u4e0b\uff0c\uff08+\uff09-6d<\/strong>\u80fd\u4ee5\u8f83\u9ad8\u7684\u5bf9\u6620\u9009\u62e9\u6027\u8f6c\u5316\u4e3a\uff08-\uff09-7d<\/strong>\uff08Scheme 4\uff09\u3002<\/p>\n <\/p>\n \u5927\u5bb6\u6240\u719f\u77e5\u7684\u8054\u82b3\u57fa\u5316\u5408\u7269\u7684\u52a8\u529b\u5b66\u62c6\u5206\u673a\u7406\u4e3a\uff1a\u78b1\u6027\u4f5c\u7528\u4e0b\u751f\u6210\u7684\u4e2d\u95f4\u4f536<\/strong>\u7684\u9178\u6027Ca<\/sub>-H\u4f1a\u53d1\u751f\u53bb\u8d28\u5b50\u5316\u4f5c\u7528\uff0c\u7136\u540e\u53d1\u751fNO2<\/sub>\u6d88\u9664\u53cd\u5e94\u5f97\u52303H<\/em>-\u5421\u54af9<\/strong>\u30029<\/strong>\u518d\u53d1\u751f\u82b3\u6784\u5316\u53cd\u5e94\u4f1a\u8f6c\u5316\u4e3a7<\/strong>\u3002\u4f46\u5f53DBU\u6216Cs2<\/sub>CO3<\/sub>\u4e3a\u78b1\u65f6\uff0c9<\/strong>\u7684Csp3<\/sup>-Csp2<\/sup>\u952e\u5bb9\u6613\u65cb\u8f6c\uff0c\u5bfc\u81f4\u4ea7\u7269\u90e8\u5206\u6d88\u65cb\u5316\uff08Scheme 5a\uff09\u3002\u5728\u6b64\u57fa\u7840\u4e0a\uff0c\u4f5c\u8005\u901a\u8fc7\u5b9e\u9a8c\u89c2\u5bdf\u63a8\u6d4b\u8be5\u53cd\u5e94\u53ef\u80fd\u7684\u673a\u7406\uff1a\u50ac\u5316\u5242\u7684\u786b\u8132\u57fa\u56e2\u53ef\u4e0e\u785d\u57fa\u5f62\u6210H-\u952e\uff0c\u4ece\u800c\u4f7fB\u7684\u53d4\u80fa\u57fa\u79bbCb<\/sub>-H\u8db3\u591f\u8fd1\u3002\u5728\u50ac\u5316\u5242B\u7684\u4f5c\u7528\u4e0b\uff0c\u50ac\u5316\u5242-6\u590d\u5408\u4f53\u53d1\u751f\u987a\u5f0f\u6d88\u9664\u751f\u62102H<\/em>-\u5421\u54af10<\/strong>\uff0c\u7d27\u63a5\u7740\u53d1\u751f\u82b3\u6784\u5316\u53cd\u5e94\u8f6c\u5316\u4e3a7<\/strong>\u3002\u7a7a\u95f4\u4f4d\u963b\u4f5c\u7528\u4f1a\u963b\u788d10\u7684Csp2<\/sup>-Csp2<\/sup>\u952e\u65cb\u8f6c\uff0c\u56e0\u6b64\uff0c\u8be5\u53cd\u5e94\u7684\u5916\u6d88\u65cb\u5316\u53ef\u964d\u5230\u6700\u4f4e\uff08Scheme 5b\uff09\u3002<\/p>\n <\/p>\n \u745e\u58eb\u6d1b\u6851\u8054\u90a6\u7406\u5de5\u5927\u5b66\u795d\u4ecb\u5e73\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86\u7b2c\u4e00\u4f8b\u785d\u57fa\u70ef\u70c3\u4e0e\u03b1-\u5f02\u6c30\u57fa\u4e59\u9178\u916f\u53d1\u751fBarton-Zard\u53cd\u5e94\uff0c\u5f97\u5230\u7684\u6d88\u65cb2-\u82b3\u57fa\u5421\u54af\u5728\u91d1\u9e21\u7eb3\u751f\u7269\u78b1\u884d\u751f\u53cc\u529f\u80fd\u50ac\u5316\u5242\u4f5c\u7528\u4e0b\u53ef\u987a\u5229\u7684\u53d1\u751f\u52a8\u529b\u5b66\u62c6\u5206\u8fc7\u7a0b\u3002\u8fd9\u662f\u7b2c\u4e00\u4f8b\u5916\u6d88\u65cb\u5316\u5408\u7269\u901a\u8fc7\u4e0d\u5bf9\u79f0\u82b3\u6784\u5316\u53cd\u5e94\u5b9e\u73b0\u52a8\u529b\u5b66\u62c6\u5206\uff0c\u5408\u6210\u624b\u6027\u8054\u82b3\u57fa\u5316\u5408\u7269\u7684\u62a5\u9053\u3002<\/p>\n <\/p>\n <\/p>\n<\/a><\/p>\n
\u8bba\u6587\u4f5c\u8005\u4ecb\u7ecd\uff1a<\/strong><\/h4>\n
<\/a><\/p>\n
\u6559\u80b2\u80cc\u666f<\/strong>\uff1a<\/h4>\n
\n
\u83b7\u5956\u60c5\u51b5<\/strong>\uff1a<\/h4>\n
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\u7814\u7a76\u9886\u57df<\/strong>\uff1a<\/h4>\n
\u8bba\u6587\u6982\u8981\uff1a<\/strong><\/h4>\n
<\/a><\/p>\n
<\/a><\/p>\n
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\u8bba\u6587\u603b\u7ed3\u8bc4\u4ef7\uff1a<\/strong><\/h4>\n
\u53c2\u8003\u6587\u732e\uff1a<\/strong><\/h4>\n
\n