{"id":15512,"date":"2017-09-13T06:57:15","date_gmt":"2017-09-12T22:57:15","guid":{"rendered":"\/\/www.gsbet888.com\/?p=15512"},"modified":"2019-08-02T18:52:47","modified_gmt":"2019-08-02T10:52:47","slug":"azaspiracid-1-by-d-a-evans%ef%bc%883%ef%bc%89","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/2017\/09\/azaspiracid-1-by-d-a-evans%ef%bc%883%ef%bc%89.html","title":{"rendered":"Azaspiracid-1 by D. A. Evans\uff083\uff09"},"content":{"rendered":"

\u524d\u9762\u4ecb\u7ecd\u4e86K. C. Nicolaou\u6559\u6388\u7684\u7ed3\u6784\u9274\u5b9a\u8fc7\u7a0b\u548c\u7b2c\u4e8c\u6b21\u5168\u5408\u6210\u5de5\u4f5c\uff0c\u8fd9\u6b21\u6211\u4eec\u6765\u63a5\u7740\u4ecb\u7ecdD. A. Evans\u6559\u6388\u57282007\u5e74\u7684ent-<\/em>Azaspiracid-1\u5168\u5408\u6210\u5de5\u4f5c[1]<\/sup>\u3002<\/p>\n

    \n
  1. \n

    A. Evans <\/strong>\u5168\u5408\u6210\u7814\u7a76<\/strong><\/h4>\n<\/li>\n<\/ol>\n

    1). <\/em><\/strong>\u9006\u5408\u6210\u5206\u6790<\/em><\/strong><\/h4>\n

    Evans\u6559\u6388\u6839\u636e\u4e4b\u524d\u5408\u6210altohyrtin C[2]<\/sup>\u548cbryostatin 2[3]<\/sup>\u7684\u5408\u6210\u7ecf\u9a8c\uff0c\u5728C-20\u4f4d\u8bbe\u8ba1\u4e86\u919b96\u4e0e\u03b1-\u70f7\u6c27\u57fa\u78fa\u9178\u76d097\u7684\u5076\u8054\u53cd\u5e94\uff0c\u4f46\u5728C-20\u4f4d\u7684\u7acb\u4f53\u9009\u62e9\u6027\u5374\u6709\u5f88\u5927\u7684\u56f0\u96be\uff0c\u4e8e\u662f\u8003\u8651\u7f9f\u57fa\u53ef\u4ee5\u901a\u8fc7\u5148\u6c27\u5316\u540e\u8fd8\u539f\u7684\u65b9\u6cd5\u5f97\u5230\u5e0c\u671b\u7684\u6784\u578b\uff0c\u5728\u6700\u540e\u7684\u5408\u6210\u4e2d\u6709\u6240\u4f53\u73b0\u3002\u919b96\u7684\u87ba\u73af\u540c\u7406\u53ef\u4ee5\u4ece\u4e4b\u524d\u7684\u6587\u732e\u627e\u5bfb\u5f97\u7528Lewis\u9178\u50ac\u5316\u5f62\u6210[4]<\/sup>\uff1b99\u901a\u8fc7\u5b98\u80fd\u56e2\u8f6c\u5316\u53cd\u5e94\u53ef\u5f97\u523098\uff0c\u800c99\u53ef\u901a\u8fc7\u788e\u7247100\u548c101\u53cd\u5e94\u5f97\u5230[5]<\/sup>\u300297\u53ef\u7531\u901a\u8fc7\u70ed\u529b\u5b66\u63a7\u5236\u4e0b\u7684\u4e00\u7cfb\u5217\u6210\u73af\u53cd\u5e94\u5f97\u5230\uff1b102\u5219\u901a\u8fc7aldol\u53cd\u5e94\u5f97\u5230\u3002<\/p>\n

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

    \u56fe1\uff1aEvans<\/em>\u2019<\/em>Retrosynthetic Analysis of ent-Azaspiracid-1<\/em><\/p>\n

    2). ent-Azaspiracid-1<\/em><\/strong>\u7684\u5168\u5408\u6210<\/em><\/strong><\/h4>\n

    A<\/em><\/strong>\uff1aABCD\u73af\u4f53\u7cfb\u7684\u5408\u6210<\/em><\/strong><\/p>\n

    \u5982\u56fe2\u6240\u793a\uff0c\u70ef\u4e19\u9187115\u7684\u5408\u6210\u662f\u7531107\u548c110\u4e24\u4e2a\u7247\u6bb5\u62fc\u63a5\u800c\u6210\u7684\u3002\u5728107\u7684\u5408\u6210\u4e2d\uff0c\u4e19\u70ef\u916e105\u5148\u4e0e\u82ef\u786b\u915a\u52a0\u6210\u5f97\u5230\u7684\u786b\u919a106\u63a5\u7740\u4e0e\u4e19\u4e8c\u70ef\u683c\u5f0f\u8bd5\u5242\u53cd\u5e94\u5f97\u5230\u9ad8\u7094\u4e19\u9187107\uff1b\u5e95\u7269108\u4e0e109\u5728Grubbs-Hoveyda \u2161 \u7684\u50ac\u5316\u4e0b\u53d1\u751f\u70ef\u70c3\u590d\u5206\u89e3\u53cd\u5e94<\/a>\u5f97weinreb\u9170\u80fa110\uff1b\u4e24\u5f53\u91cf\u4e01\u57fa\u9502\u5904\u7406\u7684\u9ad8\u7094\u4e19\u9187107\u4e0e110\u53cd\u5e94\u5f97\u5230\u7684112\u7ecf\u7f9f\u57fa\u4fdd\u62a4\u540e\u5f97113\uff0c\u7531\u4e8eweinreb\u9170\u80fa\u7684\u914d\u4f4d\u7a33\u5b9a\u4f5c\u7528\uff0c\u7fb0\u57fa\u4e0d\u4f1a\u88ab\u8fc7\u5ea6\u8fd8\u539f\uff1b113\u7ecf114\u6240\u793a\u8fc7\u6e21\u6001\uff0c\u7ecf\u5386CBS Reduction<\/a>\u5f97\u5230115[6]<\/sup>\u3002<\/p>\n

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

    \u56fe2\uff1a Evans\u2018 Synthesis of Allylic Alcohol 115<\/em><\/p>\n

    \u70ef\u4e19\u9187115\u5728Lindlar\u50ac\u5316\u5242\u4f5c\u7528\u4e0b\u88ab\u9009\u62e9\u6027\u8fd8\u539f\u6210\u987a\u5f0f\u70ef\u70c3\uff0c\u63a5\u7740\u7528TBSCl\u4fdd\u62a4\u7f9f\u57fa\u5f97116\uff1b\u5f31\u78b1\u6027\u6761\u4ef6\u4e0b\u8131\u9664\u4e59\u9170\u57fa\u540e\u6c27\u5316\u6b64\u7f9f\u57fa\u5f97\u916e117\uff1b117\u5148\u8131TBS\u4fdd\u62a4\u57fa\u540e\u5728\u9178\u6027\u6761\u4ef6\u4e0b\u5173A\u73af\u5f97\u82ef\u786b\u919a118\uff1b118\u88ab\u6c27\u5316\u5f97\u5230\u781c119\uff1b119\u672c\u662f\u5f53\u521d\u8bbe\u60f3\u7684\u5076\u8054\u788e\u7247\uff0c\u4f46\u5728\u53cd\u5e94\u65f6\u4ea7\u7387\u4e0d\u9ad8\uff0c\u4e8e\u662f\u5c06\u916f\u57fa\u8fd8\u539f\u6210\u7f9f\u57fa\u5e76\u7528Si\u4fdd\u62a4\uff0c\u770b\u4f3c\u65e0\u5173\u7d27\u8981\u7684\u53d8\u5316\uff0c\u6539\u53d8\u4e86\u8ddd\u79bb\u781c\u57fa\u7684\u8ddd\u79bb\uff0c\u8fd9\u5728\u540e\u9762\u7684\u53cd\u5e94\u4e2d\u53ef\u4ee5\u770b\u51fa\uff0c\u5bf9\u4ea7\u7387\u6709\u8f83\u5927\u5f71\u54cd\u3002<\/p>\n

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

    \u56fe3\uff1a Evans\u2018 Synthesis of A-Ring Sulfone 101<\/em><\/p>\n

    \u5728D\u73af\u788e\u7247100\u7684\u5408\u6210\u4e2d\u9996\u5148\u8fd0\u7528\u5230\u4e86\u4e0d\u5bf9\u79f0\u7684 hetero-ene reaction<\/em>\u4ee3\u66ffaldol reaction\u5f97\u5230\u9ad8\u70ef\u4e19\u9187124\uff0c123\u4e0e120\u7684\u4e24\u4e2a\u6c27\u914d\u4f4d\u5f62\u6210\u7684\u4e0d\u7a33\u5b9a\u5e73\u9762\u5bfc\u81f4\u4e86\u53cd\u5e94\u7684\u9ad8\u9009\u62e9\u6027\uff1b\u916f\u57fa\u88abweinreb\u9170\u80fa\u53d6\u4ee3\uff0c\u7f9f\u57fa\u7528PMB<\/em>\u4fdd\u62a4<\/em><\/a>\u5f97weinreb\u9170\u80fa125\uff1b\u53d1\u751flithium-halogen exchange<\/em><\/a>\u7684126\u4e0e125\u53cd\u5e94\u8131\u53bb\u80fa\u90e8\u5206\u540e\u5f97127\uff1b127\u4e2d\u7684\u7fb0\u57fa\u7ecfFelkin-Anh Reduction<\/em>[7]<\/sup>\u9ad8\u9009\u62e9\u6027\u7684\u5f97\u5230\u9187129\uff1b\u5728\u7b2c\u4e00\u6b65\u5f97\u5230\u7684\u70ef\u70c3\u7ecf\u81ed\u6c27\u6c27\u5316\u5f97\u5230\u916e\uff0c\u968f\u540e\u5728\u9178\u7684\u50ac\u5316\u4e0b\u7f9f\u57fa\u4e0e\u5f62\u6210\u7684\u7fb0\u57fa\u53cd\u5e94\u5173\u4e0aD\u73af\uff0c\u5f62\u6210\u7f29\u916e131\uff0c\u968f\u540e\u8131\u9664\u7532\u6c27\u57fa\u540e\u5f97\u5230\u671f\u671b\u7684\u53cd\u5f0f\u56db\u6c22\u544b\u5583\u5f02\u6784\u4f53\uff0c\u5176\u4e2d\u6b64\u53cd\u5e94\u7684\u7acb\u4f53\u9009\u62e9\u6027\u5bf9\u7acb\u4f53\u73af\u5883\u6709\u7ec6\u81f4\u7684\u8981\u6c42[8]<\/sup>\uff0c\u5f53\u7f9f\u57fa\u4e3aPMB\u57fa\u56e2\u4fdd\u62a4\u65f6\uff0c\u5bf9\u7acb\u4f53\u63a7\u5236\u6709\u91cd\u8981\u4f5c\u7528\uff1b\u968f\u540e\u8131\u9664PMB\u57fa\u56e2\uff0c\u7f9f\u57fa\u7528TES\u91cd\u65b0\u57fa\u56e2\u4fdd\u62a4\u5f97\u5230\u7f29\u916e133\uff0c\u518d\u7ecf\u8fc7\u5355\u7535\u5b50\u8fd8\u539f\u5242LiDBB\u8131\u9664\u82c4\u57fa\u4fdd\u62a4[9]<\/sup>\uff0c\u6700\u540e\u7ecfParikh-Doering<\/em><\/a>\u6c27\u5316\u5f97\u5230D\u73af\u788e\u7247100\u3002<\/p>\n

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

    \u56fe4\uff1a Evans\u2018 Synthesis of D-Ring Aldehyde 100<\/em><\/p>\n

    101\u5728LDA\u7684\u4f5c\u7528\u4e0b\u8131\u8d28\u5b50\u540e\u4e0e\u919b100\u53cd\u5e94\u5f97\u56db\u79cd\u5f02\u6784\u4f5399[5]<\/sup>\uff0c\u968f\u540e\u5c06\u5f62\u6210\u7684\u7f9f\u57fa\u7ecfDess-Martin Oxidation<\/a>\u6c27\u5316\u6210\u7fb0\u57fa\uff0c\u5e76\u5728\u8fd8\u539f\u6761\u4ef6\u4e0b\u8131\u9664\u781c\u57fa\u5f97\u5355\u4e00\u5316\u5408\u726998\uff1bTBAF\u8131\u9664Si\u4fdd\u62a4\u540e\u5173C\u73af\uff0c\u518d\u7ecfPPTS(cat.)\u50ac\u5316\u5f62\u6210B\u73af\uff0c\u5f97\u5230\u87ba\u7f29\u916e136\uff1b\u6700\u540e\u5148\u8131\u9664Si\u4fdd\u62a4\u540e\u5c06\u7f9f\u57fa\u6c27\u5316\u6210\u919b\uff0c\u5f97ABCD\u73af\u4f53\u7cfb96\u3002<\/p>\n

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

    \u56fe5\uff1a Evans\u2018 Synthesis of ABCD-Ring Aldehyde 96<\/em><\/p>\n

    B<\/em><\/strong>\uff1aEFGHI\u73af\u4f53\u7cfb\u7684\u5408\u6210<\/em><\/strong><\/p>\n

    \u5728EFGHI\u73af\u4f53\u7cfb\u7684\u5408\u6210\u4e2d\uff0cEvans\u6559\u6388\u8bfe\u9898\u7ec4\u7684\u7bb1\u5f0f\u50ac\u5316\u5242(box catalyst)\u4e5f\u5e94\u7528\u5176\u4e2d\u3002137\u548c138\u5728\u7bb1\u5f0f\u9521\u50ac\u5316\u5242(tin \u2161 box catalyst)\u50ac\u5316\u4e0b\u53d1\u751fMukaiyama Aldol Reaction<\/em><\/a>\uff0c\u9ad8\u9009\u62e9\u6027\u7684\u751f\u6210\u53cd\u5f0faldol\u4ea7\u7269141[10, 11]<\/sup>\uff0cCu\u7684d\u7535\u5b50\u5c42\u7535\u5b50\u4e3ad9<\/sup>\uff0c\u53ef\u4ee5\u5f62\u6210\u5e73\u9762\u7684\u914d\u4f4d\u5f62\u5f0f\uff0c\u800cSn\u7684d\u5c42\u7535\u5b50\u5168\u5145\u6ee1\uff0c\u6545\u91c7\u53d6\u56db\u9762\u4f53\u5f0f\u7684\u914d\u4f4d\u65b9\u5f0f\uff0c\u5982140\u6240\u793a\u3002\u4e3a\u4e86\u51cf\u5c0f\u544b\u5583\u6c27\u4e0e\u919b\u6c27\u7684\u7535\u6027\u6392\u65a5\u4f5c\u7528\uff0c\u91c7\u7528140\u6240\u793a\u7684\u65b9\u5f0f\uff0c\u9ad8\u9009\u62e9\u6027\u5f97\u5230141\uff1b\u8fd8\u539f\u03b1,\u03b2-\u4e0d\u9971\u548c\u5185\u916f\u7684\u78b3\u78b3\u53cc\u952e\uff0c\u7f9f\u57fa\u7528PMB\u4fdd\u62a4\u5f97\u5185\u916f143\uff1b143\u7ecf\u8fd8\u539f\u5f00\u73af[12]<\/sup>\u5f97\u5230\u7684\u7f9f\u57fa\u968f\u540e\u7528TBS\u4fdd\u62a4\uff0c\u6700\u540e\u8131\u9664\u4e00\u4e2a\u7f9f\u57fa\u4e0a\u7684\u4fdd\u62a4\uff0c\u5f97\u4e00\u7ea7\u9187145\uff1b\u4e00\u7ea7\u9187145\u5148\u4e0eTsCl\u53cd\u5e94\u7684OTs\u57fa\uff0c\u968f\u540e\u88ab\u6c30\u57fa\u53d6\u4ee3\u5f97146\uff1bBoc\u9178\u9150\u4e0e\u4e8c\u7ea7\u80fa\u53cd\u5e94\u7684\u4ea7\u7269\u968f\u540e\u88ab\u787c\u6c22\u5316\u9502\u8fd8\u539f\u6210\u4e3a\u4e00\u7ea7\u9187148\uff1b\u518d\u5c06\u9187\u7528TMS\u4fdd\u62a4\u540e\uff0c\u7532\u57fa\u9502\u8fd8\u539f\u6c30\u57fa\uff0c\u5e76\u5728\u540e\u5904\u7406\u4e2d\u4e00\u5e76\u8131\u9664TMS\u4fdd\u62a4\u57fa\u5f97\u5230\u7684\u916e149\uff1b\u6700\u540e149\u7684\u7f9f\u57fa\u7ecfParikh-Doering<\/em>\u6c27\u5316\uff0c\u88ab\u6c27\u5316\u6210\u919b\u57fa\u5f97103\u3002<\/p>\n

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

    \u56fe6\uff1a Evans\u2018 Synthesis of Aldehyde Fragment 103<\/em><\/p>\n

    150\u548c151\u5728\u4e8c\u4ef7\u94dc\u7bb1\u5f0f\u50ac\u5316\u5242\uff08Cu(\u2161) box catalyst 152\uff09\u50ac\u5316\u4e0b\u53d1\u751f\u4e0d\u5bf9\u79f0\u7684\u6c27\u6742D-A\u53cd\u5e94\uff08hetero-Diels-Alder[<\/sup><\/em><\/a>32]<\/sup><\/em>\uff09\u9ad8\u9009\u62e9\u6027\u5f97\u5230\u4e8c\u6c22\u5421\u5583\u4ea7\u7269154\uff0c\u7531153\u53ef\u4ee5\u770b\u51fa\uff0c\u4e3a\u6d88\u9664\u5e73\u9762\u4e0a\u7684\u4f4d\u963b\u5f71\u54cd\uff0c150\u9009\u62e9\u4ece\u4e0b\u9762\u53cd\u5e94\uff0c\u5f97\u5230\u4ea7\u7269\uff1b\u4e8c\u6c22\u5421\u5583154\u4ece\u4f4d\u963b\u66f4\u5c0f\u7684\u9762\u88ab\u8fd8\u539f\u5f97\u5230\u56db\u6c22\u5421\u5583155\uff1b\u56db\u6c22\u5421\u5583\u5728\u9178\u50ac\u5316\u4e0b\u4e0e\u82ef\u786b\u915a\u53cd\u5e94\uff0c\u5f97\u5230\u6784\u578b\u8f6c\u53d8\u7684O,S-<\/em>\u6742\u7f29\u916e156\uff1b\u968f\u540e\u5728\u78b1\u50ac\u5316\u4e0b\u53d1\u751f\u5e73\u8861\u53cd\u5e94\uff0c\u5f97\u5230\u916f\u57fa\u53cd\u8f6c\u7684\u66f4\u6709\u5229\u4ea7\u7269157\uff0c\u6700\u540e\u916f\u57fa\u88ab\u8fd8\u539f\u6210\u919b\u57fa\u5f97E\u73af\u788e\u7247\u919b104\u3002<\/p>\n

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

    \u56fe7\uff1a Evans\u2018 Synthesis of E-Ring Aldehyde Fragment 104<\/em><\/p>\n

    \u5728\u5408\u6210\u788e\u7247ent<\/em>-33\u7684\u5408\u6210\u4e2d\uff0c\u662f\u4ee5\u4e2d\u95f4\u4ea7\u726955\u4e3a\u8d77\u59cb\u539f\u6599\u7684\uff0c55\u5148\u7528Si\u6c22\u8131\u9664\u4e59\u6c27\u57fa\u5f97\u5230\u7684158\u518d\u7528\u56db\u6c22\u94dd\u9502\u8fd8\u539f\u5f97\u5230\u4e00\u7ea7\u9187159\uff0c\u7136\u540e\u5c06\u7f9f\u57fa\u7528I\u7f6e\u6362\uff0c\u5f97\u5230\u7898\u5316\u7269160\uff1b\u7898\u5316\u7269\u5148\u8fdb\u884clithium-halogen\u4ea4\u6362\u5f97\u8fc7\u6e21\u6001161\uff0c\u968f\u5373\u5f00\u73af\u5f97\u5230\u70f7\u6c27\u8d1f\u79bb\u5b50\uff0c\u968f\u540e\u88abTsCl\u6355\u83b7\u5f97\u7532\u82ef\u78fa\u9178\u76d0162\uff1b162\u53d1\u751fWacker Oxidation<\/em><\/a>\uff0c\u53cc\u952e\u88ab\u6c27\u5316\u6210\u7fb0\u57fa\uff0c\u5f97\u5230\u916e163\uff1b163\u7684OTs\u57fa\u88ab\u53e0\u6c2e\u53d6\u4ee3\u5f97\u5230ent<\/em>-33\uff1bent-33<\/em>\uff0c103\u53ca104\u9700\u8981\u7528\u4e24\u4e2aaldol\u53cd\u5e94\u5c06\u5176\u94fe\u63a5\u8d77\u6765\uff0c\u63a5\u4e0a\u800c\u6765\uff0cent<\/em>-33\u5148\u751f\u6210\u70ef\u57fa\u7845\u919a164\uff0c\u968f\u540e\u4e0e103\u53d1\u751fMukaiyama Aldol<\/em><\/a>\u53cd\u5e94\uff0c\u7ecf\u8fc7\u4e2d\u95f4\u8fc7\u6e21\u6001165\uff0c\u5f97\u5230aldol\u4ea7\u7269166\u3002<\/p>\n

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

    \u56fe8\uff1a Evans<\/em>\u2019<\/em> Synthesis of Methyl Ketone ent-33, and Its Coupling with Aldehyde 103<\/em><\/p>\n

    \u53e6\u5916\u4e00\u4e2aaldol\u53cd\u5e94\u662f\u7532\u57fa\u916e166\u4e0e\u919b104\u53d1\u751f\u7684Paterson Aldol\u53cd\u5e94\u3002\u7532\u57fa\u916e166\u5148\u53bb\u8d28\u5b50\u540e\u4e0e\u787c\u7ed3\u5408\u751f\u6210\u70ef\u9187\u5f0f\uff0c\u968f\u540e\u4e0e\u919b104\u53d1\u751f\u53cd\u5e94\u5f97\u5230102\uff0c\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8fd9\u91cc\u7684\u9009\u62e9\u6027\u5e76\u4e0d\u662f\u5f88\u597d\uff0860\uff1a40 dr<\/em>\uff09\uff0c\u8fd9\u662f\u7f3a\u5c11\u53ef\u4ee5\u534f\u52a9\u53cd\u5e94\u7684\u5b98\u80fd\u56e2\u53c2\u4e0e\u53cd\u5e94\u5bfc\u81f4\u7684\u3002\u5b9e\u9645\u4e0a\uff0c\u8fd9\u79cd\u76f4\u63a5\u7684\u7b56\u7565\u5bf9\u8fd94\u4e2aC=O\u53cc\u952e\u7684\u53cd\u5e94\u6027\u8fdb\u884c\u4e86\u4ed4\u7ec6\u8003\u91cf\uff0c\u5728\u7cbe\u5fc3\u8bbe\u8ba1\u7684\u8def\u7ebf\u4e0b\uff0c\u624d\u6709\u53ef\u80fd\u5b8c\u62103\u4e2a\u788e\u7247\u7684\u62fc\u63a5\u3002<\/p>\n

    \u788e\u7247\u5076\u8054\u4ea7\u7269102\u5728HF\u4e2d\u8131Si\u4fdd\u62a4\u57fa\u540e\uff0c\u540c\u65f6\u53d1\u751fGF\u73af\u7684\u73af\u5316\uff0c\u5f97\u5230EFG\u73af\u5316\u5408\u7269167\uff1b\u7528Dess-Martin\u6c27\u5316\uff0c\u5c06\u4ef2\u7f9f\u57fa\u6c27\u5316\u6210\u7fb0\u57fa\u540e\uff0cDDQ\u8131\u9664PMB\u4fdd\u62a4\u57fa\u5f97169\uff1b\u5728Pd\/C\uff0cH2<\/sub>\u4e2d\uff0c\u53e0\u6c2e\u88ab\u8fd8\u539f\u6210\u77ac\u65f6\u7684\u6c28\u57fa\uff0c\u7acb\u523b\u53d1\u751f\u73af\u5316\u53cd\u5e94\uff0c\u5f97HI\u73af170\uff1b\u4e2d\u95f4\u4f53170\u7684\u6c28\u57fa\u5148\u88abTeoc\u4fdd\u62a4\u57fa\u4fdd\u62a4\u540e\uff0c\u968f\u540e\u5728Tebbe Reagent<\/em><\/a>[14]<\/sup><\/em>\u7684\u50ac\u5316\u4e0b\uff0c\u7fb0\u57fa\u8f6c\u6362\u6210\u53cc\u952e\uff0c\u5f97\u5230\u70ef\u70c3171\uff0c\u6700\u540e\u5c06\u82ef\u786b\u919a\u6c27\u5316\u6210\u781c97\u3002<\/p>\n

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

    \u56fe9\uff1a Evans\u2018 Synthesis of EFGHI-Ring Sulfone 97<\/em><\/p>\n

     <\/p>\n

    C<\/em><\/strong>\uff1a\u788e\u7247\u8fde\u63a5\u53ca\u5168\u5408\u6210<\/em><\/strong><\/p>\n

    \u5982\u56fe10\u6240\u793a\uff0c\u03b1-\u70f7\u6c27\u57fa\u781c97\u5148\u88ab\u4e01\u57fa\u9502\u53bb\u8d28\u5b50\uff0c\u968f\u540e\u4e0e\u919b96\u53d1\u751fsulfone-aldehyde<\/em>\u53cd\u5e94[5]<\/sup>\u5f97\u5230\u4e2d\u95f4\u8fc7\u6e21\u6001172\uff0c\u7528NaOAc\/AcOH\u5904\u7406\uff0c\u4f7f\u781c\u57fa\u8131\u53bb\u4ee5\u53ca\u6c27\u8d1f\u79bb\u5b50\u5f97\u8d28\u5b50\uff0c\u5f97\u523027% 173\u548c23% 174\uff1bC-20\u4f4d\u7684\u6784\u578b\u53ef\u901a\u8fc7\u6c27\u5316\u8fd8\u539f\u7684\u65b9\u6cd5\u626d\u8f6c\uff0c\u4e8e\u662f173\u5148\u53d1\u751fSwern Oxidation<\/em><\/a>\uff0c\u540e\u7528\u56db\u6c22\u94dd\u9502\u8fd8\u539f\u5f97\u5230\u671f\u671b\u7684174\uff1bTBAF\u8131\u4fdd\u62a4\u57fa\u5f97\u5230\u7684175\u7ecf\u4e24\u6b65\u6c27\u5316\uff08Dess-Martin Oxidation & Pinnick Oxidation\uff09\uff0c\u5c06\u7f9f\u57fa\u8f6c\u53d8\u6210\u7fa7\u57fa\uff0c\u5f97\u5230\u4ea7\u7269ent-<\/em>Azaspiracid-1\uff0c\u5b8c\u6210\u5168\u5408\u6210\u3002<\/p>\n

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

    \u56fe10\uff1aFinal Stages and Sompletion of Evans\u2018 Total Synthesis of ent-Azaspiracid-1<\/em><\/p>\n

     <\/p>\n

      \n
    1. \n

      \u603b\u7ed3<\/strong><\/h4>\n<\/li>\n<\/ol>\n

      \u590d\u6742\u5206\u5b50\u7684\u5168\u5408\u6210\u5728\u5bf9azaspiracid\u7684\u63a2\u7d22\u4e2d\u8d77\u7740\u91cd\u8981\u7684\u4f5c\u7528\uff0c\u8fd9\u4e0d\u4ec5\u662f\u5728\u5bf9\u5176\u7ed3\u6784\u7684\u6d4b\u5b9a\u4e2d\uff0c\u5bf9\u751f\u7406\u6d3b\u6027\u7814\u7a76\u4e5f\u63d0\u4f9b\u4e86\u5ba2\u89c2\u7684\u4f9b\u5e94\u91cf\u3002\u5728\u8fd9\u5176\u4e2d\u7684\u4e00\u4e9b\u5408\u6210\u5de5\u4f5c\u4e5f\u4e3a\u65b0\u7684\u5929\u7136\u4ea7\u7269\u7ed3\u6784\u9274\u5b9a\u63d0\u4f9b\u4e86\u65b0\u65b9\u6cd5\uff0c\u4e5f\u4e3a\u63a2\u7d22\u8fd9\u4e9b\u751f\u7269\u6bd2\u7d20\u7684\u4f5c\u7528\u673a\u7406\u63d0\u4f9b\u4e86\u5e2e\u52a9\u3002\u6b63\u5982\u524d\u9762\u7ae0\u8282\u6240\u8bb2\uff0c\u5168\u5408\u6210\u5728\u5316\u5b66\u548c\u751f\u7269\u9274\u5b9a\u65b0\u7684\u5929\u7136\u4ea7\u7269\u4e2d\uff0c\u7279\u522b\u5b9e\u5728\u7f3a\u5c11\u8db3\u591f\u7684\u5929\u7136\u4ea7\u7269\u539f\u6599\u65f6\uff0c\u8d77\u7740\u81f3\u5173\u91cd\u8981\u7684\u4f5c\u7528\uff0c\u3002<\/p>\n

       <\/p>\n

      \u53c2\u8003\u6587\u732e<\/em><\/strong><\/h4>\n
        \n
      1. a) D. A. Evans, L. Kv\u00e6rn\u00f8, J. A. Mulder, B. Raymer, T. B. Dunn, A. Beauchemin, E. J. Olhava, M. Juhl, K. Kagechika, Angew. Chem. Int. Ed.,<\/em> 2007, 46<\/em>, 4693<\/a>; b) D. A. Evans, L. Kv\u00e6rn\u00f8, J. A. Mulder, B. Raymer, T. B. Dunn, A. Beauchemin, E. J. Olhava, M. Juhl, K. Kagechika, Angew. Chem. Int. Ed.,<\/em> 2007, 46<\/em>, 4698<\/a>; c) D. A. Evans, L. Kv\u00e6rn\u00f8, T. B. Dunn, A. Beauchemin, B. Raymer, J. A. Mulder, E. J. Olhava, M. Juhl, K. Kagechika, D. A. Favor, J. Am. Chem. Soc.,<\/em> 2008, 130<\/em>, 16295<\/a>;<\/li>\n
      2. (a) A. Evans, B. W. Trotter, B. C\u00f4t\u00e9, P. J. Coleman, Angew. Chem. Int. Ed. Engl<\/em>. 1997. 36<\/em>, 2737. DOI: 10.1002\/anie.199727381<\/a> (b) D. A. Evans, B. W. Trotter, B. C\u00f4t\u00e9, P. J. Coleman, Angew. Chem. Int. Ed. Engl.<\/em> 1997. 36<\/em>, 2741. DOI: 10.1002\/anie.199727411<\/a> (c) D. A. Evans, B. W. Trotter, B. C\u00f4t\u00e9, P. J. Coleman, Angew. Chem. Int. Ed. Engl<\/em>. 1997. 36<\/em>, 2744. DOI: 10.1002\/anie.199727441<\/a> (d) David A. Evans, B.Wesley Trotter, Paul J. Coleman, Bernard C\u00f4t\u00e9, Luiz Carlos Dias, Hemaka A. Rajapakse, Andrew N. Tyler, Tetrahedron<\/em>, 1999, 55<\/em>, 8671. DOI.org\/10.1016\/S0040-4020(99)00438-X<\/a>;<\/li>\n
      3. (a) A. Evans, P. H. Carter, E. M. Carreira, J. A. Prunet, A. B. Charette, M. Lautens,Angew. Chem. Int. Ed.<\/em> 1998, 37<\/em>, 2354. DOI: 10.1002\/(SICI)1521-3773(19980918)37<\/a> (b) D. A. Evans, P. H. Carter, E. M. Carreira, J. A. Prunet, A. B. Charette, M. Lautens, J. Am. Chem. Soc.,<\/em> 1999, 121<\/em>. 7540. DOI: 10.1021\/ja990860j<\/a>;<\/li>\n
      4. Margaret A. Brimblea, Far\u00e8s A. Far\u00e8sb, Tetrahedron<\/em>, 1999, 55<\/em>, 7661 org\/10.1016\/S0040-4020(99)00387-7<\/a>;<\/li>\n
      5. (a) L. Field, J.<\/em>\u00a0Am. Chem. Soc., <\/em>1952, 74<\/em>. 3919. DOI: 10.1021\/ja01135a062<\/a>. (b) L. Field, J. W. McFarland, J. Am. Chem. Soc.,<\/em> 1953, 75<\/em>. 5582. DOI: 10.1021\/ja01118a031<\/a>;<\/li>\n
      6. J. Corey, C. J. Helal, Angew. Chem. Int. Ed.<\/em> 1998, 37<\/em>, 1986. DOI: 10.1002\/(SICI)1521-3773(19980817)37<\/a>;<\/li>\n
      7. For a review on models for stereoinduction, see: A. Mengel, O. Reiser, Chem.<\/em>\u00a0Rev.,<\/em> 1999, 99<\/em>, 1191. DOI: 10.1021\/cr980379w<\/a>;<\/li>\n
      8. H. Larsen, B. H. Ridgway, J. T. Shaw, K. A. Woerpel, J. Am. Chem. Soc.,<\/em> 1999, 121<\/em>, 12208. DOI: 10.1021\/ja993349z<\/a>;<\/li>\n
      9. (a) P. K. Freeman, L. L. Hutchinson,\u00a0J. Org. Chem.,<\/em> 1980, 45<\/em>, 1924. DOI: 10.102 1\/jo01298a034<\/a>. (a) P. K. Freeman, L. L. Hutchinson, J. Org. Chem.,<\/em> 1983, 48<\/em>, 4705, DOI: 10.1021 \/jo00172a049<\/a>;<\/li>\n
      10. For a review on Mukaiyama aldol reaction, see: Mukaiyama, T. Angew.\u00a0Chem. Int. Ed.\u00a0<\/em>2004<\/strong>,\u00a043<\/em>, 5590. doi:10.1002\/anie.200300641<\/a>;<\/li>\n
      11. A. Evans, M. C. Kozlowski, J. A. Murry, C. S. Burgey, K. R. Campos, B. T. Connell, R. J. Staples, J. Am. Chem. Soc.,<\/em> 1999, 121<\/em>, 669. DOI: 10.1021\/ja9829822<\/a>;<\/li>\n
      12. For a review on metal hydride reductants, see: H. C. Brown, S. Krishnamurthy, Tetrahedron<\/em>, 1979, 35, 567. org\/10.1016\/0040-4020(79)87003-9<\/a>;<\/li>\n
      13. For a review on asymmetric hetero-Diels-Alder cycloaddition of carbonyl componds, see: H. Pellissier, Tetrahedron<\/em>, 2009, 65<\/em>, 2839. org\/10.1016\/j.tet.2009.01.068<\/a>;<\/li>\n
      14. Tebbe, F. N.; Parshall, G. W.; Reddy, G. S. J.\u00a0Am. Chem. Soc.<\/em>, 1978, 100<\/em>, 3611. DOI:10.1021\/ja00479a061<\/a>;<\/li>\n<\/ol>\n

         <\/p>\n

        \u672c\u6587\u7248\u6743\u5c5e\u4e8e\u00a0Chem-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":"\u524d\u9762\u4ecb\u7ecd\u4e86K. C. Nicolaou\u6559\u6388\u7684\u7ed3\u6784\u9274\u5b9a\u8fc7\u7a0b\u548c\u7b2c\u4e8c\u6b21\u5168\u5408\u6210\u5de5\u4f5c\uff0c\u8fd9\u6b21\u6211\u4eec\u6765\u63a5\u7740\u4ecb\u7ecdD. A. Evans\u6559\u6388\u57282007\u5e74\u7684ent-Azaspiracid-1\u5168\u5408\u6210\u5de5\u4f5c[1]\u3002 A. Evans \u5168\u5408\u6210\u7814\u7a76 1). \u9006\u5408\u6210\u5206\u6790 Evans\u6559\u6388\u6839\u636e\u4e4b\u524d\u5408\u6210altohyrtin C[2]\u548cbryostatin 2[3]\u7684\u5408\u6210\u7ecf\u9a8c\uff0c\u5728C-20\u4f4d\u8bbe\u8ba1\u4e86\u919b96\u4e0e\u03b1-\u70f7\u6c27\u57fa\u78fa\u9178\u76d097\u7684\u5076\u8054\u53cd\u5e94\uff0c\u4f46\u5728C-20\u4f4d\u7684\u7acb\u4f53\u9009\u62e9\u6027\u5374\u6709\u5f88\u5927\u7684\u56f0\u96be\uff0c\u4e8e\u662f\u8003\u8651\u7f9f\u57fa\u53ef\u4ee5\u901a\u8fc7\u5148\u6c27\u5316\u540e\u8fd8\u539f\u7684\u65b9\u6cd5\u5f97\u5230\u5e0c\u671b\u7684\u6784\u578b\uff0c\u5728\u6700\u540e\u7684\u5408\u6210\u4e2d\u6709\u6240\u4f53\u73b0\u3002\u919b96\u7684\u87ba\u73af\u540c\u7406\u53ef\u4ee5\u4ece\u4e4b\u524d\u7684\u6587\u732e\u627e\u5bfb\u5f97\u7528Lewis\u9178\u50ac\u5316\u5f62\u6210[4]\uff1b99\u901a\u8fc7\u5b98\u80fd\u56e2\u8f6c\u5316\u53cd\u5e94\u53ef\u5f97\u523098\uff0c\u800c99\u53ef\u901a\u8fc7\u788e\u7247100\u548c101\u53cd\u5e94\u5f97\u5230[5]\u300297\u53ef\u7531\u901a\u8fc7\u70ed\u529b\u5b66\u63a7\u5236\u4e0b\u7684\u4e00\u7cfb\u5217\u6210\u73af\u53cd\u5e94\u5f97\u5230\uff1b102\u5219\u901a\u8fc7aldol\u53cd\u5e94\u5f97\u5230\u3002 \u56fe1\uff1aEvans\u2019Retrosynthetic Analysis of ent-Azaspiracid-1 2). ent-Azaspiracid-1\u7684\u5168\u5408\u6210 A\uff1aABCD\u73af\u4f53\u7cfb\u7684\u5408\u6210 \u5982\u56fe2\u6240\u793a\uff0c\u70ef\u4e19\u9187115\u7684\u5408\u6210\u662f\u7531107\u548c110\u4e24\u4e2a\u7247\u6bb5\u62fc\u63a5\u800c\u6210\u7684\u3002\u5728107\u7684\u5408\u6210\u4e2d\uff0c\u4e19\u70ef\u916e105\u5148\u4e0e\u82ef\u786b\u915a\u52a0\u6210\u5f97\u5230\u7684\u786b\u919a106\u63a5\u7740\u4e0e\u4e19\u4e8c\u70ef\u683c\u5f0f\u8bd5\u5242\u53cd\u5e94\u5f97\u5230\u9ad8\u7094\u4e19\u9187107\uff1b\u5e95\u7269108\u4e0e109\u5728Grubbs-Hoveyda \u2161 \u7684\u50ac\u5316\u4e0b\u53d1\u751f\u70ef\u70c3\u590d\u5206\u89e3\u53cd\u5e94\u5f97weinreb\u9170\u80fa110\uff1b\u4e24\u5f53\u91cf\u4e01\u57fa\u9502\u5904\u7406\u7684\u9ad8\u7094\u4e19\u9187107\u4e0e110\u53cd\u5e94\u5f97\u5230\u7684112\u7ecf\u7f9f\u57fa\u4fdd\u62a4\u540e\u5f97113\uff0c\u7531\u4e8eweinreb\u9170\u80fa\u7684\u914d\u4f4d\u7a33\u5b9a\u4f5c\u7528\uff0c\u7fb0\u57fa\u4e0d\u4f1a\u88ab\u8fc7\u5ea6\u8fd8\u539f\uff1b113\u7ecf114\u6240\u793a\u8fc7\u6e21\u6001\uff0c\u7ecf\u5386CBS Reduction\u5f97\u5230115[6]\u3002 \u56fe2\uff1a Evans\u2018 Synthesis of Allylic Alcohol 115 \u70ef\u4e19\u9187115\u5728Lindlar\u50ac\u5316\u5242\u4f5c\u7528\u4e0b\u88ab\u9009\u62e9\u6027\u8fd8\u539f\u6210\u987a\u5f0f\u70ef\u70c3\uff0c\u63a5\u7740\u7528TBSCl\u4fdd\u62a4\u7f9f\u57fa\u5f97116\uff1b\u5f31\u78b1\u6027\u6761\u4ef6\u4e0b\u8131\u9664\u4e59\u9170\u57fa\u540e\u6c27\u5316\u6b64\u7f9f\u57fa\u5f97\u916e117\uff1b117\u5148\u8131TBS\u4fdd\u62a4\u57fa\u540e\u5728\u9178\u6027\u6761\u4ef6\u4e0b\u5173A\u73af\u5f97\u82ef\u786b\u919a118\uff1b118\u88ab\u6c27\u5316\u5f97\u5230\u781c119\uff1b119\u672c\u662f\u5f53\u521d\u8bbe\u60f3\u7684\u5076\u8054\u788e\u7247\uff0c\u4f46\u5728\u53cd\u5e94\u65f6\u4ea7\u7387\u4e0d\u9ad8\uff0c\u4e8e\u662f\u5c06\u916f\u57fa\u8fd8\u539f\u6210\u7f9f\u57fa\u5e76\u7528Si\u4fdd\u62a4\uff0c\u770b\u4f3c\u65e0\u5173\u7d27\u8981\u7684\u53d8\u5316\uff0c\u6539\u53d8\u4e86\u8ddd\u79bb\u781c\u57fa\u7684\u8ddd\u79bb\uff0c\u8fd9\u5728\u540e\u9762\u7684\u53cd\u5e94\u4e2d\u53ef\u4ee5\u770b\u51fa\uff0c\u5bf9\u4ea7\u7387\u6709\u8f83\u5927\u5f71\u54cd\u3002 \u56fe3\uff1a Evans\u2018 Synthesis of A-Ring Sulfone 101 \u5728D\u73af\u788e\u7247100\u7684\u5408\u6210\u4e2d\u9996\u5148\u8fd0\u7528\u5230\u4e86\u4e0d\u5bf9\u79f0\u7684 hetero-ene reaction\u4ee3\u66ffaldol reaction\u5f97\u5230\u9ad8\u70ef\u4e19\u9187124\uff0c123\u4e0e120\u7684\u4e24\u4e2a\u6c27\u914d\u4f4d\u5f62\u6210\u7684\u4e0d\u7a33\u5b9a\u5e73\u9762\u5bfc\u81f4\u4e86\u53cd\u5e94\u7684\u9ad8\u9009\u62e9\u6027\uff1b\u916f\u57fa\u88abweinreb\u9170\u80fa\u53d6\u4ee3\uff0c\u7f9f\u57fa\u7528PMB\u4fdd\u62a4\u5f97weinreb\u9170\u80fa125\uff1b\u53d1\u751flithium-halogen exchange\u7684126\u4e0e125\u53cd\u5e94\u8131\u53bb\u80fa\u90e8\u5206\u540e\u5f97127\uff1b127\u4e2d\u7684\u7fb0\u57fa\u7ecfFelkin-Anh Reduction[7]\u9ad8\u9009\u62e9\u6027\u7684\u5f97\u5230\u9187129\uff1b\u5728\u7b2c\u4e00\u6b65\u5f97\u5230\u7684\u70ef\u70c3\u7ecf\u81ed\u6c27\u6c27\u5316\u5f97\u5230\u916e\uff0c\u968f\u540e\u5728\u9178\u7684\u50ac\u5316\u4e0b\u7f9f\u57fa\u4e0e\u5f62\u6210\u7684\u7fb0\u57fa\u53cd\u5e94\u5173\u4e0aD\u73af\uff0c\u5f62\u6210\u7f29\u916e131\uff0c\u968f\u540e\u8131\u9664\u7532\u6c27\u57fa\u540e\u5f97\u5230\u671f\u671b\u7684\u53cd\u5f0f\u56db\u6c22\u544b\u5583\u5f02\u6784\u4f53\uff0c\u5176\u4e2d\u6b64\u53cd\u5e94\u7684\u7acb\u4f53\u9009\u62e9\u6027\u5bf9\u7acb\u4f53\u73af\u5883\u6709\u7ec6\u81f4\u7684\u8981\u6c42[8]\uff0c\u5f53\u7f9f\u57fa\u4e3aPMB\u57fa\u56e2\u4fdd\u62a4\u65f6\uff0c\u5bf9\u7acb\u4f53\u63a7\u5236\u6709\u91cd\u8981\u4f5c\u7528\uff1b\u968f\u540e\u8131\u9664PMB\u57fa\u56e2\uff0c\u7f9f\u57fa\u7528TES\u91cd\u65b0\u57fa\u56e2\u4fdd\u62a4\u5f97\u5230\u7f29\u916e133\uff0c\u518d\u7ecf\u8fc7\u5355\u7535\u5b50\u8fd8\u539f\u5242LiDBB\u8131\u9664\u82c4\u57fa\u4fdd\u62a4[9]\uff0c\u6700\u540e\u7ecfParikh-Doering\u6c27\u5316\u5f97\u5230D\u73af\u788e\u7247100\u3002 \u56fe4\uff1a Evans\u2018 Synthesis of D-Ring Aldehyde 100 101\u5728LDA\u7684\u4f5c\u7528\u4e0b\u8131\u8d28\u5b50\u540e\u4e0e\u919b100\u53cd\u5e94\u5f97\u56db\u79cd\u5f02\u6784\u4f5399[5]\uff0c\u968f\u540e\u5c06\u5f62\u6210\u7684\u7f9f\u57fa\u7ecfDess-Martin Oxidation\u6c27\u5316\u6210\u7fb0\u57fa\uff0c\u5e76\u5728\u8fd8\u539f\u6761\u4ef6\u4e0b\u8131\u9664\u781c\u57fa\u5f97\u5355\u4e00\u5316\u5408\u726998\uff1bTBAF\u8131\u9664Si\u4fdd\u62a4\u540e\u5173C\u73af\uff0c\u518d\u7ecfPPTS(cat.)\u50ac\u5316\u5f62\u6210B\u73af\uff0c\u5f97\u5230\u87ba\u7f29\u916e136\uff1b\u6700\u540e\u5148\u8131\u9664Si\u4fdd\u62a4\u540e\u5c06\u7f9f\u57fa\u6c27\u5316\u6210\u919b\uff0c\u5f97ABCD\u73af\u4f53\u7cfb96\u3002 \u56fe5\uff1a Evans\u2018 Synthesis of ABCD-Ring Aldehyde 96 B\uff1aEFGHI\u73af\u4f53\u7cfb\u7684\u5408\u6210 \u5728EFGHI\u73af\u4f53\u7cfb\u7684\u5408\u6210\u4e2d\uff0cEvans\u6559\u6388\u8bfe\u9898\u7ec4\u7684\u7bb1\u5f0f\u50ac\u5316\u5242(box catalyst)\u4e5f\u5e94\u7528\u5176\u4e2d\u3002137\u548c138\u5728\u7bb1\u5f0f\u9521\u50ac\u5316\u5242(tin \u2161 box catalyst)\u50ac\u5316\u4e0b\u53d1\u751fMukaiyama Aldol Reaction\uff0c\u9ad8\u9009\u62e9\u6027\u7684\u751f\u6210\u53cd\u5f0faldol\u4ea7\u7269141[10, 11]\uff0cCu\u7684d\u7535\u5b50\u5c42\u7535\u5b50\u4e3ad9\uff0c\u53ef\u4ee5\u5f62\u6210\u5e73\u9762\u7684\u914d\u4f4d\u5f62\u5f0f\uff0c\u800cSn\u7684d\u5c42\u7535\u5b50\u5168\u5145\u6ee1\uff0c\u6545\u91c7\u53d6\u56db\u9762\u4f53\u5f0f\u7684\u914d\u4f4d\u65b9\u5f0f\uff0c\u5982140\u6240\u793a\u3002\u4e3a\u4e86\u51cf\u5c0f\u544b\u5583\u6c27\u4e0e\u919b\u6c27\u7684\u7535\u6027\u6392\u65a5\u4f5c\u7528\uff0c\u91c7\u7528140\u6240\u793a\u7684\u65b9\u5f0f\uff0c\u9ad8\u9009\u62e9\u6027\u5f97\u5230141\uff1b\u8fd8\u539f\u03b1,\u03b2-\u4e0d\u9971\u548c\u5185\u916f\u7684\u78b3\u78b3\u53cc\u952e\uff0c\u7f9f\u57fa\u7528PMB\u4fdd\u62a4\u5f97\u5185\u916f143\uff1b143\u7ecf\u8fd8\u539f\u5f00\u73af[12]\u5f97\u5230\u7684\u7f9f\u57fa\u968f\u540e\u7528TBS\u4fdd\u62a4\uff0c\u6700\u540e\u8131\u9664\u4e00\u4e2a\u7f9f\u57fa\u4e0a\u7684\u4fdd\u62a4\uff0c\u5f97\u4e00\u7ea7\u9187145\uff1b\u4e00\u7ea7\u9187145\u5148\u4e0eTsCl\u53cd\u5e94\u7684OTs\u57fa\uff0c\u968f\u540e\u88ab\u6c30\u57fa\u53d6\u4ee3\u5f97146\uff1bBoc\u9178\u9150\u4e0e\u4e8c\u7ea7\u80fa\u53cd\u5e94\u7684\u4ea7\u7269\u968f\u540e\u88ab\u787c\u6c22\u5316\u9502\u8fd8\u539f\u6210\u4e3a\u4e00\u7ea7\u9187148\uff1b\u518d\u5c06\u9187\u7528TMS\u4fdd\u62a4\u540e\uff0c\u7532\u57fa\u9502\u8fd8\u539f\u6c30\u57fa\uff0c\u5e76\u5728\u540e\u5904\u7406\u4e2d\u4e00\u5e76\u8131\u9664TMS\u4fdd\u62a4\u57fa\u5f97\u5230\u7684\u916e149\uff1b\u6700\u540e149\u7684\u7f9f\u57fa\u7ecfParikh-Doering\u6c27\u5316\uff0c\u88ab\u6c27\u5316\u6210\u919b\u57fa\u5f97103\u3002 \u56fe6\uff1a Evans\u2018 Synthesis of Aldehyde Fragment 103 150\u548c151\u5728\u4e8c\u4ef7\u94dc\u7bb1\u5f0f\u50ac\u5316\u5242\uff08Cu(\u2161) box catalyst 152\uff09\u50ac\u5316\u4e0b\u53d1\u751f\u4e0d\u5bf9\u79f0\u7684\u6c27\u6742D-A\u53cd\u5e94\uff08hetero-Diels-Alder[32]\uff09\u9ad8\u9009\u62e9\u6027\u5f97\u5230\u4e8c\u6c22\u5421\u5583\u4ea7\u7269154\uff0c\u7531153\u53ef\u4ee5\u770b\u51fa\uff0c\u4e3a\u6d88\u9664\u5e73\u9762\u4e0a\u7684\u4f4d\u963b\u5f71\u54cd\uff0c150\u9009\u62e9\u4ece\u4e0b\u9762\u53cd\u5e94\uff0c\u5f97\u5230\u4ea7\u7269\uff1b\u4e8c\u6c22\u5421\u5583154\u4ece\u4f4d\u963b\u66f4\u5c0f\u7684\u9762\u88ab\u8fd8\u539f\u5f97\u5230\u56db\u6c22\u5421\u5583155\uff1b\u56db\u6c22\u5421\u5583\u5728\u9178\u50ac\u5316\u4e0b\u4e0e\u82ef\u786b\u915a\u53cd\u5e94\uff0c\u5f97\u5230\u6784\u578b\u8f6c\u53d8\u7684O,S-\u6742\u7f29\u916e156\uff1b\u968f\u540e\u5728\u78b1\u50ac\u5316\u4e0b\u53d1\u751f\u5e73\u8861\u53cd\u5e94\uff0c\u5f97\u5230\u916f\u57fa\u53cd\u8f6c\u7684\u66f4\u6709\u5229\u4ea7\u7269157\uff0c\u6700\u540e\u916f\u57fa\u88ab\u8fd8\u539f\u6210\u919b\u57fa\u5f97E\u73af\u788e\u7247\u919b104\u3002 \u56fe7\uff1a Evans\u2018 Synthesis of E-Ring Aldehyde Fragment 104 \u5728\u5408\u6210\u788e\u7247ent-33\u7684\u5408\u6210\u4e2d\uff0c\u662f\u4ee5\u4e2d\u95f4\u4ea7\u726955\u4e3a\u8d77\u59cb\u539f\u6599\u7684\uff0c55\u5148\u7528Si\u6c22\u8131\u9664\u4e59\u6c27\u57fa\u5f97\u5230\u7684158\u518d\u7528\u56db\u6c22\u94dd\u9502\u8fd8\u539f\u5f97\u5230\u4e00\u7ea7\u9187159\uff0c\u7136\u540e\u5c06\u7f9f\u57fa\u7528I\u7f6e\u6362\uff0c\u5f97\u5230\u7898\u5316\u7269160\uff1b\u7898\u5316\u7269\u5148\u8fdb\u884clithium-halogen\u4ea4\u6362\u5f97\u8fc7\u6e21\u6001161\uff0c\u968f\u5373\u5f00\u73af\u5f97\u5230\u70f7\u6c27\u8d1f\u79bb\u5b50\uff0c\u968f\u540e\u88abTsCl\u6355\u83b7\u5f97\u7532\u82ef\u78fa\u9178\u76d0162\uff1b162\u53d1\u751fWacker Oxidation\uff0c\u53cc\u952e\u88ab\u6c27\u5316\u6210\u7fb0\u57fa\uff0c\u5f97\u5230\u916e163\uff1b163\u7684OTs\u57fa\u88ab\u53e0\u6c2e\u53d6\u4ee3\u5f97\u5230ent-33\uff1bent-33\uff0c103\u53ca104\u9700\u8981\u7528\u4e24\u4e2aaldol\u53cd\u5e94\u5c06\u5176\u94fe\u63a5\u8d77\u6765\uff0c\u63a5\u4e0a\u800c\u6765\uff0cent-33\u5148\u751f\u6210\u70ef\u57fa\u7845\u919a164\uff0c\u968f\u540e\u4e0e103\u53d1\u751fMukaiyama Aldol\u53cd\u5e94\uff0c\u7ecf\u8fc7\u4e2d\u95f4\u8fc7\u6e21\u6001165\uff0c\u5f97\u5230aldol\u4ea7\u7269166\u3002 \u56fe8\uff1a Evans\u2019 Synthesis of Methyl Ketone ent-33, and Its Coupling with Aldehyde 103 \u53e6\u5916\u4e00\u4e2aaldol\u53cd\u5e94\u662f\u7532\u57fa\u916e166\u4e0e\u919b104\u53d1\u751f\u7684Paterson Aldol\u53cd\u5e94\u3002\u7532\u57fa\u916e166\u5148\u53bb\u8d28\u5b50\u540e\u4e0e\u787c\u7ed3\u5408\u751f\u6210\u70ef\u9187\u5f0f\uff0c\u968f\u540e\u4e0e\u919b104\u53d1\u751f\u53cd\u5e94\u5f97\u5230102\uff0c\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8fd9\u91cc\u7684\u9009\u62e9\u6027\u5e76\u4e0d\u662f\u5f88\u597d\uff0860\uff1a40 dr\uff09\uff0c\u8fd9\u662f\u7f3a\u5c11\u53ef\u4ee5\u534f\u52a9\u53cd\u5e94\u7684\u5b98\u80fd\u56e2\u53c2\u4e0e\u53cd\u5e94\u5bfc\u81f4\u7684\u3002\u5b9e\u9645\u4e0a\uff0c\u8fd9\u79cd\u76f4\u63a5\u7684\u7b56\u7565\u5bf9\u8fd94\u4e2aC=O\u53cc\u952e\u7684\u53cd\u5e94\u6027\u8fdb\u884c\u4e86\u4ed4\u7ec6\u8003\u91cf\uff0c\u5728\u7cbe\u5fc3\u8bbe\u8ba1\u7684\u8def\u7ebf\u4e0b\uff0c\u624d\u6709\u53ef\u80fd\u5b8c\u62103\u4e2a\u788e\u7247\u7684\u62fc\u63a5\u3002 \u788e\u7247\u5076\u8054\u4ea7\u7269102\u5728HF\u4e2d\u8131Si\u4fdd\u62a4\u57fa\u540e\uff0c\u540c\u65f6\u53d1\u751fGF\u73af\u7684\u73af\u5316\uff0c\u5f97\u5230EFG\u73af\u5316\u5408\u7269167\uff1b\u7528Dess-Martin\u6c27\u5316\uff0c\u5c06\u4ef2\u7f9f\u57fa\u6c27\u5316\u6210\u7fb0\u57fa\u540e\uff0cDDQ\u8131\u9664PMB\u4fdd\u62a4\u57fa\u5f97169\uff1b\u5728Pd\/C\uff0cH2\u4e2d\uff0c\u53e0\u6c2e\u88ab\u8fd8\u539f\u6210\u77ac\u65f6\u7684\u6c28\u57fa\uff0c\u7acb\u523b\u53d1\u751f\u73af\u5316\u53cd\u5e94\uff0c\u5f97HI\u73af170\uff1b\u4e2d\u95f4\u4f53170\u7684\u6c28\u57fa\u5148\u88abTeoc\u4fdd\u62a4\u57fa\u4fdd\u62a4\u540e\uff0c\u968f\u540e\u5728Tebbe Reagent[14]\u7684\u50ac\u5316\u4e0b\uff0c\u7fb0\u57fa\u8f6c\u6362\u6210\u53cc\u952e\uff0c\u5f97\u5230\u70ef\u70c3171\uff0c\u6700\u540e\u5c06\u82ef\u786b\u919a\u6c27\u5316\u6210\u781c97\u3002 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