{"id":37317,"date":"2021-03-09T08:00:44","date_gmt":"2021-03-09T00:00:44","guid":{"rendered":"\/\/www.gsbet888.com\/?p=37317"},"modified":"2021-03-05T23:28:34","modified_gmt":"2021-03-05T15:28:34","slug":"%e4%b8%ad%e7%a7%91%e9%99%a2%e5%b9%bf%e5%b7%9e%e7%94%9f%e7%89%a9%e5%8c%bb%e8%8d%af%e4%b8%8e%e5%81%a5%e5%ba%b7%e7%a0%94%e7%a9%b6%e9%99%a2%e9%82%b1%e5%8f%91%e6%b4%8b%e8%af%be%e9%a2%98%e7%bb%84angew","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2021\/03\/%e4%b8%ad%e7%a7%91%e9%99%a2%e5%b9%bf%e5%b7%9e%e7%94%9f%e7%89%a9%e5%8c%bb%e8%8d%af%e4%b8%8e%e5%81%a5%e5%ba%b7%e7%a0%94%e7%a9%b6%e9%99%a2%e9%82%b1%e5%8f%91%e6%b4%8b%e8%af%be%e9%a2%98%e7%bb%84angew.html","title":{"rendered":"\u4e2d\u79d1\u9662\u5e7f\u5dde\u751f\u7269\u533b\u836f\u4e0e\u5065\u5eb7\u7814\u7a76\u9662\u90b1\u53d1\u6d0b\u8bfe\u9898\u7ec4Angew\uff1a (-)-Daphenylline\u548c (-)-Himalensine A\u7684\u5168\u5408\u6210"},"content":{"rendered":"

\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749<\/strong><\/p>\n

\u5bfc\u8bfb<\/h4>\n

\u8fd1\u65e5\uff0c\u4e2d\u79d1\u9662\u5e7f\u5dde\u751f\u7269\u533b\u836f\u4e0e\u5065\u5eb7\u7814\u7a76\u9662\u90b1\u53d1\u6d0b\u8bfe\u9898\u7ec4\u5728Angew. Chem. Int. Ed<\/i><\/em>.\u4e0a\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e86\u4e00\u79cd\u53ef\u5feb\u901f\u6784\u5efa\u864e\u76ae\u6960\u751f\u7269\u78b1\uff08Daphniphyllum alkaloids\uff09\u6838\u5fc3\u9aa8\u67b6\u7684\u6709\u6548\u7b56\u7565\uff0c\u53ef\u5206\u522b\u901a\u8fc716\u6b65\u548c19\u6b65\u5b8c\u6210(-)-daphenylline\u548c(-)-himalensine\u00a0A\u7684\u5168\u5408\u6210\u3002<\/p>\n

A General Strategy for the Construction of Calyciphylline A type Alkaloids: Divergent Total Syntheses of (-)-Daphenylline and (-)-Himalensine A<\/p>\n

FayangQiu, Bingyang Wang, Bo Xu, Wen Xun, YimingGuo, and Jing Zhang<\/p>\n

Angew. Chem. Int. Ed<\/i><\/em>.\u00a0ASAP DOI:10.1002\/anie.202016212<\/u><\/a><\/p><\/blockquote>\n

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\"\"\"\"<\/a><\/p>\n

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\u603b\u7ed3<\/h4>\n

\u4e2d\u79d1\u9662\u5e7f\u5dde\u751f\u7269\u533b\u836f\u4e0e\u5065\u5eb7\u7814\u7a76\u9662\u90b1\u53d1\u6d0b\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86\u4e00\u79cd\u53ef\u5feb\u901f\u6784\u5efa\u864e\u76ae\u6960\u751f\u7269\u78b1\uff08Daphniphyllum alkaloids\uff09\u6838\u5fc3\u9aa8\u67b6\u7684\u6709\u6548\u4e14\u901a\u7528\u7b56\u7565\uff0c\u4ee5(S<\/i><\/em>)-\u9999\u82b9\u916e18<\/b><\/strong>\u4e3a\u521d\u59cb\u5e95\u7269\uff0c\u5206\u522b\u901a\u8fc716\u6b65\u548c19\u6b65\u5b8c\u6210\u4e86(-)-daphenylline\u548c(-)-himalensine\u00a0A\u7684\u5168\u5408\u6210\u3002\u540c\u65f6\uff0c\u901a\u8fc7Cu\u50ac\u5316\u5206\u5b50\u5185\u73af\u4e19\u70f7\u5316\u548c\u968f\u540e\u81a6\u50ac\u5316Cope\u91cd\u6392\uff0c\u4ee5\u5408\u6210healensine A\u9aa8\u67b6\uff0c\u901a\u8fc7Diels-Alder\/\u82b3\u9999\u5316\u4ee5\u5408\u6210(-)-daphenylline\u82b3\u9999\u9aa8\u67b6\u3002<\/p>\n

\u53c2\u8003\u6587\u732e<\/h4>\n[1] a) R. B. Ruggeri, M. M. Hansen, C. H. Heathcock, J. Am. Chem. Soc.<\/i><\/em>\u00a0<\/i><\/em>1988<\/b><\/strong>, 110<\/i><\/em>, 8734-8736; b) R. B. Ruggeri, K. F. Mcclure, C. H.\u00a0<\/i><\/em>Heathcock, J. Am. Chem. Soc. <\/i><\/em>1989<\/b><\/strong>, 111<\/i><\/em>, 1530-1531; c) S. Piettre, C.\u00a0<\/i><\/em>H. Heathcock, Science <\/i><\/em>1990<\/b><\/strong>, 248<\/i><\/em>, 1532-1534; d) R. B. Ruggeri, C. H.\u00a0<\/i><\/em>Heathcock, J. Org. Chem. <\/i><\/em>1990<\/b><\/strong>, 55<\/i><\/em>, 3714-3715; e) J. A. Stafford, C. H.\u00a0<\/i><\/em>Heathcock, J. Org. Chem. <\/i><\/em>1990<\/b><\/strong>, 55<\/i><\/em>, 5433-5434; f) C. H. Heathcock,\u00a0<\/i><\/em>Angew.Chem. Int. Ed. Engl. <\/i><\/em>1992<\/b><\/strong>, 31<\/i><\/em>, 665-681; g) C. H. Heathcock, S.\u00a0<\/i><\/em>K. Davidsen, S. G. Mills, M. A. Sanner, J. Org. Chem. <\/i><\/em>1992<\/b><\/strong>, 57<\/i><\/em>, 2531-2544; h) C. H. Heathcock, M. M. Hansen, R. B. 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Chem. Int. Ed.\u4e0a\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e86\u4e00\u79cd\u53ef\u5feb\u901f\u6784\u5efa\u864e\u76ae\u6960\u751f\u7269\u78b1\uff08Daphniphyllum alkaloids\uff09\u6838\u5fc3\u9aa8\u67b6\u7684\u6709\u6548\u7b56\u7565\uff0c\u53ef\u5206\u522b\u901a\u8fc716\u6b65\u548c19\u6b65\u5b8c\u6210(-)-daphenylline\u548c(-)-himalensine\u00a0A\u7684\u5168\u5408\u6210\u3002 A General Strategy for the Construction of Calyciphylline A type Alkaloids: Divergent Total Syntheses of (-)-Daphenylline and (-)-Himalensine A FayangQiu, Bingyang Wang, Bo Xu, Wen Xun, YimingGuo, and Jing Zhang Angew. Chem. Int. Ed.\u00a0ASAP DOI:10.1002\/anie.202016212 \u6b63\u6587 \u65e9\u5728110\u5e74\u524d\uff0c\u7814\u7a76\u8005\u5c31\u5df2\u5bf9\u690d\u7269\u4e2d\u7684\u864e\u76ae\u6960\u751f\u7269\u78b1\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u7814\u7a76\uff0c\u5176\u4e2dYagi\u7b49\u9996\u6b21\u4eceD. macropodum\u4e2d\u5206\u79bb\u51fa\u4e00\u79cdC30\u578b\u864e\u76ae\u6960\u751f\u7269\u78b1daphnimacrine\uff0c\u4f46\u76f4\u52301966\u5e74Hirata\u7b49\u901a\u8fc7X-\u5c04\u7ebf\u6676\u4f53\u5b66\u624d\u786e\u5b9a\u6b64\u7ed3\u6784\u3002\u6b64\u540e\uff0c\u5df2\u4ece\u864e\u76ae\u6960\u751f\u7269\u78b1\u5c5e\u4e2d\u5206\u79bb\u51fa320\u591a\u79cd\u751f\u7269\u78b1\u3002\u57fa\u4e8e\u9aa8\u67b6\u7684\u591a\u6837\u6027\uff0c\u864e\u76ae\u6960\u751f\u7269\u78b1\u53ef\u5206\u4e3a20\u591a\u79cd\u7c7b\u578b\u3002\u540c\u65f6\uff0c\u6b64\u7c7b\u751f\u7269\u78b1\u5177\u6709\u590d\u6742\u7684\u6c2e\u6742\u591a\u73af\u78b3\u9aa8\u67b6\uff08Figure 1\uff09\u3002\u6b64\u5916\uff0c\u864e\u76ae\u6960\u751f\u7269\u78b1\u5177\u6709\u5e7f\u6cdb\u7684\u751f\u7269\u5b66\u6d3b\u6027\uff0c\u5982\u6297\u764c\u3001\u6297HIV\u3001\u6297\u6c27\u5316\u548c\u8840\u7ba1\u8212\u5f20\u6d3b\u6027\u3002\u57281986\u5e74\u81f31995\u5e74\u671f\u95f4\uff0cHeathcock\u7b49[1]\u5b8c\u6210\u4e86\u51e0\u9879\u975e\u5e38\u51fa\u8272\u7684\u5168\u5408\u6210\u3002\u968f\u540e\uff0c\u4e5f\u6709\u8fd1\u4e8c\u5341\u4e2a\u8bfe\u9898\u7ec4\u4e5f\u62a5\u9053\u76f8\u5173\u7814\u7a76\u5de5\u4f5c\u3002\u5c3d\u7ba1\u5df2\u53d6\u5f97\u4e00\u5b9a\u5730\u8fdb\u5c55\uff0c\u4f46\u4ecd\u9700\u5f00\u53d1\u4e00\u79cd\u66f4\u4e3a\u9ad8\u6548\u4e14\u901a\u7528\u7684\u5408\u6210\u864e\u76ae\u6960\u751f\u7269\u78b1\u7684\u7b56\u7565\u3002 2003\u5e74\uff0cKobayashi\u7b49[2]\u62a5\u9053\u4e86calyciphylline\u00a0A\u578b\u9aa8\u67b6\u53ef\u80fd\u6e90\u4e8eyuzurimine A\u578b\u751f\u7269\u78b1\u30022009\u5e74\uff0cHao\u7b49[3]\u62a5\u9053\u4e86\u4e00\u79cd\u6d89\u53ca\u751f\u7269\u6cd5\u7684daphenylline\u5408\u6210\u9014\u5f84\u3002\u800cdaphenylline\uff084\uff09\u901a\u8fc7calyciphylline\u00a0A\u578b\u751f\u7269\u78b1Wagner-Meerwein\u73af\u6269\u5f20\u83b7\u5f97\u3002\u53d7\u6b64\u542f\u53d1\uff0cLi[4]\u548cZhai[5]\u00a0\u7b49\u5206\u522b\u62a5\u9053\u4e86daphenylline\u7684\u5168\u5408\u6210\u3002\u5c3d\u7ba1\u91cd\u6392\u4f5c\u4e3a\u5b9e\u73b0daphenylline\u5168\u5408\u6210\uff084\uff09\u7684\u6709\u6548\u7b56\u7565\uff0c\u4f46\u4f5c\u8005\u8ba4\u4e3a\uff0c\u53ef\u901a\u8fc7\u5206\u79bb\u51fa\u7684himalensine\u00a0A\uff087\uff09\u9aa8\u67b6[6]\u4f5c\u4e3a\u5408\u6210calyciphylline\u00a0A\u578b\u751f\u7269\u78b1\uff08\u5305\u62ecdaphenylline\uff09\u901a\u7528\u4e2d\u95f4\u4f53\uff0c\u4ece\u800c\u5927\u5927\u7b80\u5316\u5168\u5408\u6210\u8def\u5f84\uff08Figure 2A\uff09\u3002\u5728\u6b64\uff0c\u4f5c\u8005\u62a5\u9053\u4e86\u4ee5[3,3]-Cope\u91cd\u6392\u4e3a\u7279\u5f81\u8fdb\u884chimalensineA\u9aa8\u67b6\u7684\u5168\u5408\u6210\uff0c\u4ece\u800c\u5b9e\u73b0\u4e86(-)-daphenylline\u548c(-)-himalensine\u00a0A\u7684\u5168\u5408\u6210\u3002 \u53d7Rh\u50ac\u5316[4+3]\u73af\u52a0\u6210\u53cd\u5e94\u7684\u542f\u53d1\uff0c\u4f5c\u8005\u8bbe\u60f3\u901a\u8fc7\u73af\u4e19\u70f7\u5316\/ Cope\u91cd\u6392\u4ee5\u5408\u6210healensine A\u9aa8\u67b6\uff0811\uff09\u3002\u56e0\u6b64\uff0c\u4f5c\u8005\u8fdb\u884c\u4e86\u9006\u5408\u6210\u5206\u6790\uff08Figure 2B\uff09\u3002\u9996\u5148\uff0c\u901a\u8fc7\u4e2d\u95f4\u4f5313\u7684[3,3]-Cope\u91cd\u6392\u4ece\u800c\u5408\u6210\u4e2d\u95f4\u4f5312\uff0c\u800c\u4e2d\u95f4\u4f5313\u53ef\u901a\u8fc7\u4e2d\u95f4\u4f5314\u7684\u73af\u4e19\u70f7\u5316\u83b7\u5f97\u3002\u5bf9\u4e8e\u4e2d\u95f4\u4f5314\u7684\u5408\u6210\uff0c\u6839\u636e\u524d\u671f\u5408\u6210\u7684\u6c2e\u6742\u6865\u73af\u9aa8\u67b6[7]\uff0c\u4ee5(S)-\u9999\u82b9\u916e18\u548c\u73af\u620a\u70ef\u57fa\u7898\u5316\u726917\u4e3a\u521d\u59cb\u5e95\u7269\u8fdb\u800c\u5408\u6210\u3002 \u9996\u5148\uff0c\u4f5c\u8005\u4ee5(S)-\u9999\u82b9\u916e18\u4e3a\u521d\u59cb\u5e95\u7269\uff0c\u57fa\u4e8e\u524d\u671f\u4e24\u6b65\u5b9e\u9a8c[7]\u5408\u6210\u70ef\u4e19\u57fa\u53e0\u6c2e\u5316\u726919\u3002\u53e0\u6c2e\u5316\u726919\u4e0e\u73af\u620a\u70ef\u57fa\u9502\u7ecf1,2-\u52a0\u6210\uff0c\u7136\u540e\u7528PPh3\u8fd8\u539f\u53e0\u6c2e\u57fa\uff0c\u53ef\u5f97\u5230\u4f2f\u80fa16\uff0c\u6536\u7387\u4e3a76\uff05\u3002\u4f2f\u80fa16\u4e2d\u7684\u6c28\u57fa\u53ef\u4e0e\u53cc\u70ef\u916e15\u8fdb\u884c\u9170\u5316\u548c\u73af\u5316\uff0c\u53ef\u751f\u6210\u9170\u80fa\u963b\u8f6c\u5f02\u6784\u4f5314\uff0c\u6536\u7387\u4e3a84\uff05\u3002\u5316\u5408\u726914\u00a0\u5728\u7ecfp-ABSA\u548cDBU\u6761\u4ef6\u4e0b\u8fdb\u884cRegitz\u91cd\u6c2e\u8f6c\u79fb\u548cCu(tbs)2\u50ac\u5316\u7684\u73af\u4e19\u70f7\u5316\u53cd\u5e94\uff0c\u83b7\u5f97\u73af\u4e19\u57fa\u5185\u916f20\u3002 \u968f\u540e\uff0c\u4f5c\u8005\u5bf9\u5173\u952e\u7684himalensine\u00a0A\u9aa8\u67b6\u8fdb\u884c\u4e86\u5408\u6210\uff0c\u6d89\u53ca[3,3]-\u03c3\u91cd\u6392\u3002\u53d7Xu\u8bfe\u9898\u7ec4\u76f8\u5173\u6587\u732e\u7684\u542f\u53d1[8]\uff0c\u4f5c\u8005\u901a\u8fc7\u5bf9\u53cd\u5e94\u6761\u4ef6\u7684\u8fdb\u4e00\u6b65\u4f18\u5316\u540e\u53d1\u73b0\uff0c\u5f53\u73af\u4e19\u57fa\u5185\u916f20\u5728\u4e09\u53d4\u4e01\u57fa\u81a6\u7684\u6c2f\u82ef\u4e2d\u8fdb\u884cCope\u91cd\u6392\u65f6\uff0c\u53ef\u83b7\u5f9782\uff05\u6536\u7387\u7684\u73af\u5e9a\u70ef\u916e21\u3002\u73af\u5e9a\u70ef\u916e21\u4f7f\u7528NaBH4\u8fd8\u539f\u548cMartin\u786b\u70f7\u8131\u6c34\uff0c\u53ef\u6210\u03b1,\u00a0\u03b2-\u4e0d\u9971\u548c\u9170\u80fa22\uff0c\u6536\u7387\u4e3a81\uff05\u3002\u4e4b\u540e\uff0c\u53ef\u7528Crabtree\u50ac\u5316\u5242\u8fdb\u884c\u533a\u57df\u548c\u975e\u5bf9\u6620\u9009\u62e9\u6027\u6c22\u5316\u53cd\u5e94\uff0c\u83b7\u5f97\u5355\u4e00\u975e\u5bf9\u6620\u5f02\u6784\u4f53\u7684\u5316\u5408\u726923\uff0c\u6536\u7387\u4e3a85\uff05\u3002 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B. Ruggeri, M. M. Hansen, C. H. Heathcock, J. Am. Chem. Soc.\u00a01988, 110, 8734-8736; b) R. B. Ruggeri, K. F. Mcclure, C. H.\u00a0Heathcock, J. Am. Chem. Soc. 1989, 111, 1530-1531; c) S. Piettre, C.\u00a0H. Heathcock, Science 1990, 248, 1532-1534; d) R. B. Ruggeri, C. 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