{"id":25329,"date":"2019-05-23T10:51:36","date_gmt":"2019-05-23T02:51:36","guid":{"rendered":"\/\/www.gsbet888.com\/?p=25329"},"modified":"2019-05-23T10:51:36","modified_gmt":"2019-05-23T02:51:36","slug":"%e8%84%82%e8%82%aa%e9%86%87%e7%9a%84%e8%bf%9c%e7%ab%afcsp3-h%e8%83%ba%e5%8c%96%e5%8f%8d%e5%ba%94","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2019\/05\/%e8%84%82%e8%82%aa%e9%86%87%e7%9a%84%e8%bf%9c%e7%ab%afcsp3-h%e8%83%ba%e5%8c%96%e5%8f%8d%e5%ba%94.html","title":{"rendered":"\u8102\u80aa\u9187\u7684\u8fdc\u7aefC(sp3)-H\u80fa\u5316\u53cd\u5e94"},"content":{"rendered":"
\u6c28\u57fa\u9187\u9aa8\u67b6\u5e7f\u6cdb\u5b58\u5728\u4e8e\u5404\u79cd\u5929\u7136\u4ea7\u7269\u3001\u5177\u6709\u836f\u7406\u6d3b\u6027\u7684\u5316\u5408\u7269\u4e2d\u3002\u800c\u5408\u6210\u8be5\u9aa8\u67b6\u6700\u6709\u529b\u7684\u7b56\u7565\u5373\u8102\u80aa\u9187\u53d1\u751f\u5b9a\u5411\u4f4d\u70b9\u9009\u62e9\u6027C(sp3<\/sup>)-H\u80fa\u5316\u53cd\u5e94\u3002\u5176\u4e2d\uff0c\u6bd4\u8f83\u7ecf\u5178\u7684\u65b9\u6cd5\u5373\u5c06\u8fc7\u6e21\u91d1\u5c5e-\u6c2e\u5316\u7269\u4e2d\u95f4\u4f53A\u63d2\u5165\u5230\u8fdc\u7aef\u672a\u6d3b\u5316\u7684C(sp3<\/sup>)-H\u952e\u4e2d(Scheme 1,a<\/em>)\uff0c\u4f46\u8be5\u65b9\u6cd5\u4ec5\u5c40\u9650\u4e8e\u03b3\u548c\u03b2-\u4f4d\u5b98\u80fd\u56e2\u5316\u3002\u6700\u8fd1\uff0c\u80fd\u5728\u6e29\u548c\u6761\u4ef6\u4e0b\u4ea7\u751f\u81ea\u7531\u57fa\u4e14\u5177\u6709\u591a\u6837\u7684HAT\u53cd\u5e94\u6027\u7684\u81ea\u7531\u57fa\u53cd\u5e94\u5f15\u8d77\u5316\u5b66\u56e2\u4f53\u7684\u5e7f\u6cdb\u5173\u6ce8\u3002\u8fc4\u4eca\u4e3a\u6b62\uff0c\u57fa\u4e8e\u81ea\u7531\u57fa\u7b56\u7565\uff0c\u8102\u80aa\u9187\u53d1\u751f\u8fdc\u7aef\u4f4d\u70b9\u9009\u62e9\u6027C(sp3<\/sup>)-H\u80fa\u5316\u53cd\u5e94\u7684\u62a5\u9053\u53ea\u6709\u4e24\u4f8b\uff1aNagib\u8bfe\u9898\u7ec4[1]\u62a5\u9053\u7684\u65e0\u9700\u91d1\u5c5e\u50ac\u5316\u7684\u53ef\u89c1\u5149\u8bf1\u5bfc\u9187\u7684\u81ea\u7531\u57fa\u53cd\u5e94\uff0c\u5408\u6210\u03b2-\u6c28\u57fa\u9187\u5316\u5408\u7269(Scheme 1, b<\/em>)\u4ee5\u53caZuo\u8bfe\u9898\u7ec4[2]\u62a5\u9053\u7684\u53ef\u89c1\u5149\u8bf1\u5bfc\u5408\u6210\u03b4-\u6c28\u57fa\u9187\u5316\u5408\u7269\u7684\u81ea\u7531\u57fa\u53cd\u5e94(Scheme 1, c<\/em>)\u3002\u8fd9\u4e24\u4f8b\u81ea\u7531\u57fa\u53cd\u5e94\u4e3b\u8981\u5c40\u9650\u4e8e1,5-HAT\u81ea\u7531\u57fa\uff0c\u8fd9\u6781\u5927\u5730\u9650\u5236\u4e86\u81ea\u7531\u57fa\u53cd\u5e94\u7684\u8303\u56f4\u3002\u5728\u4e0a\u8ff0\u80cc\u666f\u7814\u7a76\u7684\u57fa\u7840\u4e0a\uff0c\u7f8e\u56fd\u4f0a\u5229\u8bfa\u4f0a\u5927\u5b66Vladimir Gevorgyan<\/a>\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86\u7b2c\u4e00\u4f8b\u65e0\u9700\u91d1\u5c5e\u50ac\u5316\u548c\u5149\u50ac\u5316\uff0c\u5728\u6e29\u548c\u7684\u78b1\u6027\u6761\u4ef6\u548c\u91cd\u6c2e\u76d0\u4f5c\u7528\u4e0b\uff0c\u8102\u80aa\u9187\u7684\u03b2-\u3001\u03b3-\u548c\u03b4-C(sp3<\/sup>)-H\u80fa\u5316\u53cd\u5e94(Scheme 1, d<\/em>)\u3002\u76f8\u5173\u7814\u7a76\u6210\u679c\u53d1\u8868\u4e8e<\/p>\n <\/p>\n Transition Metal-and Ligh-free Directed Amination of Remote UnactivatedC(sp3)-H Bonds of Alcohols<\/p>\n Kurandina\u00e0, D.; Yadagiri\u00e0, D.; Rivas\u00e0, M.; Kavun, A.; Chuentragool, P.; Hayama, K.; Gevorgyan, V. *\u00a0 J. Am. Chem. Soc. 2019, Just Accepted Manuscript<\/p>\n DOI: 10.1021\/jacs.9b04189<\/p><\/blockquote>\n Scheme 1.\u9187\u7684\u8fdc\u7a0bC-H\u80fa\u5316\u53cd\u5e94<\/p>\n <\/p>\n \u7814\u7a76\u8005\uff1a<\/strong>Vladimir Gevorgyan<\/p>\n <\/p>\n <\/p>\n <\/p>\n \u50ac\u5316\u5408\u6210\u6cd5\u7684\u5f00\u53d1\uff0cC-H\u952e\u6d3b\u5316\uff0c\u73af\u5316\u5f02\u6784\u5316\u53cd\u5e94\uff0c\u4ee5\u53ca\u5728\u590d\u6742\u5316\u5408\u7269\u5408\u6210\u65b9\u9762\u7684\u5e94\u7528\u7814\u7a76\u3002<\/p>\n Gevorgyan\u8bfe\u9898\u7ec4\u4e00\u76f4\u5728\u5f00\u53d1\u57fa\u672c\u7684\u50ac\u5316\u65b9\u6cd5\u5e76\u63a2\u7d22\u5176\u5728\u5e7f\u6cdb\u5408\u6210\u4e2d\u7684\u5e94\u7528\uff0c\u4ed6\u4eec\u4fa7\u91cd\u70b9\u5728\u673a\u7406\u63a2\u7a76\u6765\u83b7\u5f97\u63a7\u5236\u5316\u5b66\u3001\u7acb\u4f53\u9009\u62e9\u8fc7\u7a0b\u7684\u7075\u611f\u3002\u6df1\u5165\u7406\u89e3\u53cd\u5e94\u7684\u673a\u7406\u6765\u4f7f\u4ed6\u4eec\u66f4\u597d\u5730\u786e\u5b9a\u6700\u597d\u65b9\u6848\uff0c\u5e76\u62d3\u5c55\u65b0\u53cd\u5e94\u7684\u9002\u7528\u8303\u56f4\u3002<\/p>\n <\/p>\n \u4ee51a<\/strong>\u548c2a<\/strong>\u4e3a\u6a21\u677f\u5e95\u7269\uff0c\u4f5c\u8005\u5bf9\u53cd\u5e94\u6761\u4ef6\u8fdb\u884c\u53cd\u590d\u7b5b\u9009\uff0c\u786e\u5b9a\u6700\u4f73\u6761\u4ef6\u4e3a\uff08Table 1\uff09\uff1a5 equiv HCO2<\/sub>Li\u00b7H2O\u4e3a\u6700\u4f18\u78b1\uff0cDMA\/MeOH(1:1)\u4e3a\u6700\u4f18\u6eb6\u5242\uff0c\u57280 \u2103\u5230\u5ba4\u6e29\u6761\u4ef6\u4e0b\u53cd\u5e942 h,\u80fd\u4ee576%\u7684\u6536\u7387\u5f97\u5230\u76ee\u6807\u4ea7\u7269\u3002<\/p>\n Table 1. \u6761\u4ef6\u4f18\u5316<\/p>\n <\/p>\n \u5728\u6700\u4f18\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u8003\u5bdf\u4e86\u91cd\u6c2e\u76d0\u7684\u5e95\u7269\u8303\u56f4\u3002\u4e0d\u8bba\u662f\u5438\u7535\u5b50\u53d6\u4ee3\u8fd8\u662f\u7ed9\u7535\u5b50\u53d6\u4ee3\u7684\u91cd\u6c2e\u76d0\u90fd\u80fd\u5f88\u597d\u5730\u9002\u5e94\u53cd\u5e94\u6761\u4ef6\uff0c\u53ef\u4ee5\u826f\u597d\u81f3\u4f18\u79c0\u7684\u6536\u7387\u5f97\u5230\u76f8\u5e94\u4ea7\u7269\u3002\u5176\u4e2d\uff0c1a<\/strong>\u4e0e2b<\/strong>\u53cd\u5e94\uff0c\u80fd\u4ee586%\u7684\u6536\u7387\u5f97\u5230\u76f8\u5e94\u4ea7\u7269\u3002<\/p>\n \u7d27\u63a5\u7740\uff0c\u4f5c\u8005\u8003\u5bdf\u4e861<\/strong>\u548c2b<\/strong>\u7684\u53cd\u5e94\u60c5\u51b5\u3002\u5bf9\u4e8e\u5927\u90e8\u5206\u03b3\u4f4d\u4e3a\u53d4\u78b3\u624b\u6027\u4e2d\u5fc3\u7684\u5e95\u7269\u90fd\u80fd\u5f88\u597d\u7684\u9002\u5e94\u53cd\u5e94\u6761\u4ef6\uff0c\u80fd\u4ee5\u826f\u597d\u81f3\u4f18\u79c0\u7684\u6536\u7387\u5f97\u5230\u03b3-C(sp3<\/sup>)-H\u80fa\u5316\u4ea7\u7269\uff0c\u4f46R5<\/sup>\u4f4d\u4e3a\u4f2f\u9187\u3001\u80fa\u6216\u6eb4\u5316\u7269\u7684\u5e95\u7269\u5219\u4e0d\u80fd\u5f97\u5230\u76f8\u5e94\u4ea7\u7269(Scheme 2, a)\u3002\u6b64\u5916\uff0c\u4ef2\u9187\u3001\u73af\u9187\u3001\u53cc\u73af\u9187\u3001\u53d4\u9187\u4ee5\u53ca\u4f2f\u9187\u5747\u80fd\u4ee5\u8f83\u9ad8\u7684\u6536\u7387\u5f97\u5230\u52a8\u529b\u5b66\u4e0d\u592a\u652f\u6301\u7684\u03b2-C(sp3<\/sup>)-H\u80fa\u5316\u4ea7\u7269(Scheme 2, b)\u3002\u4ef2\u9187(1ao<\/strong>, 1ap<\/strong>)\u548c\u4f2f\u9187(1aq<\/strong>)\u80fd\u5f97\u5230 \u03b4\u548c\u03b3-C(sp3<\/sup>)-H\u80fa\u5316\u4ea7\u7269\u7684\u6df7\u5408\u7269\u30022o <\/sup>C\u2212H\u548c1o\u00a0<\/sup>C\u2212H\u4e5f\u80fd\u9002\u5e94\u53cd\u5e94\u6761\u4ef6\uff0c\u80fd\u4ee5\u8f83\u9ad8\u7684\u6536\u7387\u5f97\u5230\u03b2-\u548c\u03b3-C(sp3<\/sup>)-H\u80fa\u5316\u4ea7\u7269\u3002<\/p>\n Scheme 2.\u5e95\u7269\u6269\u5c55<\/p>\n <\/p>\n \u4e3a\u4e86\u8bc1\u660e\u8be5\u53cd\u5e94\u7684\u6f5c\u5728\u4ef7\u503c\uff0c\u4f5c\u8005\u505a\u4e86\u4e00\u7cfb\u5217\u7684\u884d\u751f\u53cd\u5e94\u3002\u5404\u79cd\u53d4\u73af\u4ea7\u7269\u548c\u975e\u73af\u72b6\u4ea7\u7269\u90fd\u80fd\u4ee5\u8f83\u9ad8\u7684\u6536\u7387\u8f6c\u5316\u4e3a\u76841,2-\uff0c1,3-\u548c1,4-\u6c28\u57fa\u9187\u3002\u503c\u5f97\u9ad8\u5174\u7684\u662f\uff0c\u4e8c\u7ea7\u91cd\u6c2e\u5316\u5408\u7269\u5bb9\u6613\u5f02\u6784\u6210\u8159\u8fdb\u800c\u88ab\u6c27\u5316\u4e3a\u916e\u7c7b\u5316\u5408\u7269\u3002\u916e\u7c7b\u5316\u5408\u7269\u53ef\u88ab\u8f6c\u5316\u4e3a\u4e0d\u6613\u83b7\u5f97\u7684\u4e01\u95f4\u9187\u919b\u3002<\/p>\n <\/p>\n \u7f8e\u56fd\u4f0a\u5229\u8bfa\u4f0a\u5927\u5b66Vladimir Gevorgyan\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86\u7b2c\u4e00\u4f8b\u65e0\u9700\u91d1\u5c5e\u50ac\u5316\u548c\u5149\u50ac\u5316\uff0c\u5728\u6e29\u548c\u7684\u78b1\u6027\u6761\u4ef6\u548c\u91cd\u6c2e\u76d0\u4f5c\u7528\u4e0b\uff0c\u8102\u80aa\u9187\u7684\u03b2-\u3001\u03b3-\u548c\u03b4-C(sp3<\/sup>)-H\u80fa\u5316\u53cd\u5e94\u3002\u8be5\u53cd\u5e94\u5e95\u7269\u8303\u56f4\u5e7f\uff0c\u80fd\u4ee5\u8f83\u9ad8\u7684\u6536\u7387\u5f97\u5230\u5404\u79cd\u03b2-\u3001\u03b3-\u548c\u03b4-C(sp3<\/sup>)-H\u80fa\u5316\u4ea7\u7269\u3002\u901a\u8fc7\u7b80\u5355\u7684\u884d\u751f\u53cd\u5e94\uff0c\u53ef\u4ee5\u9ad8\u6536\u7387\u5f97\u52301,2-\uff0c1,3-\u548c1,4-\u6c28\u57fa\u9187\u548c\u916e\u7c7b\u5316\u5408\u7269\u3002<\/p>\n <\/p>\n <\/p>\n<\/a><\/p>\n
\u8bba\u6587\u4f5c\u8005\u4ecb\u7ecd\uff1a<\/strong><\/h4>\n
<\/a><\/p>\n
\u7814\u7a76\u8005<\/strong>\u7ecf\u5386<\/strong><\/h4>\n
\n
\u83b7\u5956\u7ecf\u5386<\/strong><\/h4>\n
\n
\u7814\u7a76\u6982\u8981<\/strong><\/h4>\n
\u8bba\u6587\u6982\u8981\uff1a<\/strong><\/h4>\n
<\/a><\/p>\n
<\/a><\/p>\n
\u8bba\u6587\u603b\u7ed3\u8bc4\u4ef7\uff1a<\/strong><\/h4>\n
\u53c2\u8003\u6587\u732e\uff1a<\/strong><\/h4>\n
\n