{"id":15499,"date":"2017-09-07T06:52:34","date_gmt":"2017-09-06T22:52:34","guid":{"rendered":"\/\/www.gsbet888.com\/?p=15499"},"modified":"2019-08-02T18:52:47","modified_gmt":"2019-08-02T10:52:47","slug":"azaspiracid-1-by-k-c-nicolaou%ef%bc%882%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-k-c-nicolaou%ef%bc%882%ef%bc%89.html","title":{"rendered":"Azaspiracid-1 by K. C. Nicolaou\uff082\uff09"},"content":{"rendered":"

\u6295\u7a3f\u4f5c\u8005\u00a0alberto-caeiro<\/strong><\/p>\n

\u63a5\u4e0a\u4e00\u7bc7<\/a>\u800c\u6765\uff0c\u8fd9\u91cc\u5c06\u4e3b\u8981\u4ecb\u7ecd\u4e24\u4f4d\u5316\u5b66\u5bb6\u7684\u5408\u6210\u5de5\u4f5c\u3002\u9996\u5148\u4eceK. C. Nicolaou\u6559\u6388\u57282006\u5e74\u7684\u5168\u5408\u6210\u5de5\u4f5c\u5f00\u59cb\u3002<\/p>\n

Nicolaou<\/strong>\u2018s\u7684\u5168\u5408\u6210\u7814\u7a76<\/strong>[1]<\/sup><\/h4>\n

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

2006\u5e74\u7684\u5408\u6210\u5de5\u4f5c\u4e3b\u8981\u662f\u5efa\u7acb\u5728\u4e4b\u524d\u7684\u7ed3\u6784\u5206\u6790\u4e2d\u7528\u5230\u7684\u5408\u6210\u7b56\u7565\uff0c\u5e76\u4e14\u5728\u6709\u51c6\u786e\u7ed3\u6784\u7684\u57fa\u7840\u4e0a\uff0c\u8bbe\u8ba1\u4e86\u5982\u56fe1\u6240\u793a\u7684\u6539\u8fdb\u7b56\u7565\u3002\u4e3a\u4e86\u6d88\u9664E\u548cF\u73af\u4e4b\u95f4\u5076\u8054\u65f6\u7684\u4f4d\u963b\u5f71\u54cd\uff0c\u9996\u5148\u901a\u8fc7\u7898\u5316\u6210\u919a\u53cd\u5e94\u5c06G\u73af\u4eceF\u4e0a\u5207\u5272\u51fa\u6765\uff0c\u540e\u7531Still\u5076\u8054\u5373\u53ef\u5c06F\u4e0eE\u73af\u76f8\u8fde\u63a5\u8d77\u6765\uff1bD\u4e0eE\u73af\u90e8\u5206\u53ef\u901a\u8fc7\u4e8c\u5511\u70f7\u5076\u8054\u5b9e\u73b0\u6784\u5efa\uff0c\u5177\u4f53\u5982\u4e0b\u3002<\/p>\n

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

\u56fe1\uff1a Nicolaou\u2018s Retrosynthetic Analysis of Azaspiracid-1<\/em><\/p>\n

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

\u56fe2\uff1aNicolaou\u2018s Retrosynthetic Analysis of Fragment24&Vinyl Stannane 22<\/em><\/p>\n

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

A\uff1aABCDE\u73af\u4f53\u7cfb\u7684\u5408\u6210<\/em><\/strong><\/p>\n

34\u5148\u4e0e\u78f7\u9178\u76d0\u8d1f\u79bb\u5b50\u53cd\u5e94\u751f\u6210\u78f7\u53f6\u7acb\u5fb7\u7684\u524d\u4f5336\uff0c\u540e\u53d1\u751fHornery-Wadsworth-Emmons\u5076\u8054<\/a>\uff0c\u751f\u6210E\u578b\u53cc\u952e\uff1b38\u7684\u7fb0\u57fa\u8fd8\u539f\u6210\u7f9f\u57fa\u540e\u5728\u4e59\u9178\u4e2d\u8131\u9664\u7f29\u4e19\u916e\u4fdd\u62a4\uff0c\u8fd8\u539f\u65f6\u7684\u9ad8\u6548\u7acb\u4f53\u9009\u62e9\u6027\u662f\u56e0\u4e3a\u9502\u79bb\u5b50\u7684\u914d\u4f4d\u4f5c\u7528\u598239\u6240\u793a\uff1b40\u53d1\u751f\u7898\u5316\u6210\u919a\u53cd\u5e94\u5f97\u5230D\u73af\uff0c\u7ecf\u8fc741\u7684\u4e2d\u95f4\u72b6\u6001\u5f97\u523042\uff0c\u5728\u4fdd\u62a4\u4e24\u4e2a\u6e38\u79bb\u7684\u7f9f\u57fa\u540e\uff0c\u8fdb\u884c\u4fdd\u62a4\u57fa\u7684\u4ea4\u6362\uff0c\u518d\u7ecf\u8fc7Swern Oxidation<\/a>\u5373\u53ef\u5f97\u523028\uff0c\u5f53\u7136\uff0c\u5176\u4e2d\u53ef\u4ee5\u4e0d\u9700\u8981\u8fdb\u884c\u4fdd\u62a4\u57fa\u7684\u4ea4\u6362\uff0c\u4f46\u901a\u8fc7\u8fd9\u4e00\u6b65\uff0c\u524d\u4e00\u4ee3\u5408\u6210\u7b56\u7565\u4e2d\u7684\u539f\u6599\u5c31\u53ef\u4ee5\u5728\u6b64\u5f97\u5230\u5229\u7528\u3002<\/p>\n

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

\u56fe3\uff1aNicolaou\u2018s Synthesis of D-ring Aldehyde 28<\/em><\/p>\n

\u70ef\u4e19\u918747\u5728NCS\u548cMe2<\/sub>S\u4f5c\u7528\u4e0b\u539f\u4f4d\u6c2f\u4ee3\u540e\uff0c\u53d1\u751f\u4e8c\u567b\u70f7\u5076\u8054\u5f97\u523050\uff0c\u518d\u7528\u4e59\u4e8c\u9187\u4fdd\u62a4\u7fb0\u57fa\u5f9751\uff1b51\u5148\u8131TBDPS\u4fdd\u62a4\u540e\u518d\u8fdb\u884c\u7898\u4ee3\u5f9729\uff1b29\u9700\u52a02eq\u7684\u00adt<\/em>-BuLi\u8131\u9664\u7898\uff0c1\u5f53\u91cf\u7528\u4e8e\u8131\u9664\u7898\uff0c\u53e6\u4e00\u5f53\u91cf\u4f7ft<\/em>-BuI\u5f62\u6210\u5f02\u4e01\u70ef\u3001\u5f02\u4e01\u70f7\u4e0e\u7898\u5316\u9502\uff0c\u4ece\u800c\u53cd\u5e94\u80fd\u591f\u5411\u53f3\u8fdb\u884c\u5f62\u6210\u8d1f\u79bb\u5b50\uff0c\u540e\u53d1\u751fDess-Martin<\/a>\u6c27\u5316\u5f97\u523027\uff1b27\u7ecfLewis\u9178\u8bf1\u5bfc\u7684domino\u53cd\u5e94\uff0c\u901a\u8fc7\u8131\u9664TES\u57fa\u56e2\u4e0e\u4e19\u916e\u4fdd\u62a4\u57fa\uff0c\u5f62\u6210ABC\u4e09\u73af\u5f97\u5230\u768426\u5728C-10\u4f4d\u7684\u5dee\u5411\u5f02\u6784\u4f53dr<\/em>\u503c\u4e3a6\uff1a1[2]<\/sup>\uff1b26\u7aef\u57fa\u5904\u4e00\u7ea7\u9187\u6c27\u5316\u6210\u7fb0\u57fa\u540e\uff0c\u53d1\u751fWittig\u53cd\u5e94\u5f97\u523052\uff1b52\u5728Grubbs\u2161 cat. \u7684\u50ac\u5316\u4e0b\uff0c\u53d1\u751f\u70ef\u70c3\u590d\u5206\u89e3\u53cd\u5e94\u5f97\u5230ABCD\u56db\u73af\u90e8\u520654[3, 4]<\/sup>\u3002<\/p>\n

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

\u56fe4\uff1aNicolaou\u2018s Synthesis of ABCD Ring Systme 54<\/em><\/p>\n

25\u662f\u6784\u5efaE\u73af\u7684\u4e3b\u8981\u524d\u4f53\u3002\u4ece\u624b\u6027\u73af\u5185\u916f55\u51fa\u53d1\uff0c\u5148\u7ecfDIBAL-H\u8fd8\u539f\u6210\u73af\u534a\u7f29\u919b56\u540e\u5728Lewis\u9178\u50ac\u5316\u4e0b\u5f00\u73af\u5e76\u75281,3-\u4e19\u4e8c\u786b\u9187\u4fdd\u62a4\u919b\u57fa\u5f9757\uff1b\u4e00\u7ea7\u9187\u7ecfDess-Martin<\/em>\u6c27\u5316\u5f97\u919b58\u540e\uff0c\u4e0e61\u53d1\u751fNozaki-Hiyama-Kishi\u5076\u8054<\/a>\u5f9762\uff1b62\u5148\u6c27\u5316\u540e\u8fd8\u539f\u5f97\u5230\u9700\u8981\u6784\u8c61\u7684\u7f9f\u57fa64\uff1b64\u5148\u8131TBS\u4fdd\u62a4\u5f97\u52302\u9187\u540e\uff0c\u6362\u4fdd\u62a4\u57fa\u5f97\u523025<\/p>\n

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

\u56fe5\uff1aNicolaou\u2018s Synthesis of Alkyl Iodide 29<\/em><\/p>\n

54\u8131TBDPS\u4fdd\u62a4\u540e\uff0c\u5148\u540e\u7ecf\u5386Swern\u6c27\u5316<\/a>\u53caPinnick\u6c27\u5316<\/a>\u5f97\u5230\u76f8\u5e94\u7684\u7fa7\u9178\u540e\u916f\u5316\u5f9724\uff1b24\u7ecf\u4e8c\u567b\u70f7\u5076\u8054\u5f9723\u540e\uff0cDIBAL-H\u8fd8\u539f\u5f97\u5230\u7684C-20\u4f4d\u76842\u7ea7\u7f9f\u57fa\uff0cTBAF\u8131\u9664\u7f9f\u57fa\u7684\u4fdd\u62a4\u57fa\uff0c\u6700\u7ec8\u5f97\u56db\u9187\u5316\u5408\u726967\uff1b\u7528\u4e59\u9170\u6c2f\u5c06\u7aef\u7f9f\u57fa\u4fdd\u62a4\u540e\uff0c\u6c27\u5316\u6761\u4ef6\u4e0b\u8131\u9664\u4e8c\u786b\u9187\u4fdd\u62a4\u5f97\u5230\u7684\u7fb0\u57fa\u7acb\u523b\u4e0e\u6e38\u79bb\u7684\u7f9f\u57fa\u7f9f\u919b\u7f29\u5408\u5f97\u534a\u7f29\u916e\uff0c\u5b8c\u6210E\u73af\u7684\u6784\u5efa\uff0c\u5f9721\u3002<\/p>\n

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

\u56fe6\uff1aNicolaou\u2018s Synthesis of ABCDE Ring Fragment 21<\/em><\/p>\n

B\uff1aFHI\u73af\u4f53\u7cfb\u7684\u5408\u6210<\/em><\/strong><\/p>\n

FHI\u73af\u4f53\u7cfb\u7684\u5408\u6210\u9996\u5148\u4eceF\u73af\u7684\u6784\u5efa\u5f00\u59cb\u3002L-\u9152\u77f3\u9178\u62c6\u5206\u5f97\u5230\u7684\u4e8c\u918769\u5148\u5355\u4fdd\u62a4\u7f9f\u57fa\uff0cPMP\u4fdd\u62a4\u57fa\u5728\u8fd8\u539f\u6761\u4ef6\u4e0b\u5207\u65ad\u4e00\u4fa7\u7684C-O\u952e\uff0c\u5f97\u5230\u94fe\u72b6\u90bb\u4f4d\u4e8c\u918770\uff0c\u968f\u540e\u88ab\u6c27\u5316\u5f97\u5230\u919b71\uff1b71\u7ecf\u8fc7Brown Allylation<\/em>\u53cd\u5e94\u540e\u9ad8\u9009\u62e9\u6027\u7684\u5f97\u5230\u9ad8\u70ef\u4e19\u918772[5]<\/sup>\u3002\u6e38\u79bb\u7684\u7f9f\u57fa\u4e0e\u4e19\u70ef\u9178\u53d1\u751f\u916f\u5316\u53cd\u5e94\u5f9774\uff0c\u968f\u540e\u5728Grubbs\u2160\u50ac\u5316\u5242\u4e0b\u8fdb\u884c\u70ef\u70c3\u590d\u5206\u89e3\u53cd\u5e94\u5173\u73af\u5f97\u03b1,\u03b2-\u4e0d\u9971\u548c\u916f75\uff1b\u70f7\u57fa\u94dc\u9502\u8bd5\u5242\u4e0e75\u7ecf\u8fc775\u2018\u6240\u793a\u8fc7\u6e21\u6001\u53d1\u751f1,4-\u5171\u8f6d\u52a0\u6210\u5f97\u5230\u73af\u5185\u916f76\uff0c\u968f\u540e\u5728TBAF\u7684\u4f5c\u7528\u4e0b\u8131\u9664\u4fdd\u62a4\u57fa\u7684\u4e00\u7ea7\u9187\u88ab\u6c27\u5316\u6210\u919b32\u3002<\/p>\n

\u788e\u724733\u7684\u5408\u6210\u662f\u4ece\u53cd\u5f0f55\u5f00\u59cb\u7684\u3002ent-<\/em>55\u5728Lewis\u9178\u4f5c\u7528\u4e0b\u5f00\u73af\u5f97\u5230weinerb\u9170\u80fa77\uff1b77\u4e2d\u7aef\u7f9f\u57fa\u4e0eTsCl\u53cd\u5e94\u540e\uff0c\u88ab\u53e0\u6c2e\u53d6\u4ee3\u5f97\u53e0\u6c2e\u5316\u5408\u726978\uff1b78\u4e0e\u7532\u57fa\u9502\u53d1\u751f\u4eb2\u6838\u53d6\u4ee3\u5f9733\uff0c\u5176\u4e2d\u7531\u4e8e\u9502\u79bb\u5b50\u7684\u914d\u4f4d\u5f62\u6210\u7a33\u5b9a\u7684\u4e2d\u95f4\u4f5379\uff0c\u4f7f\u5f9778\u4e0d\u4f1a\u88ab\u8fd8\u539f\u8fc7\u5ea6\u5f97\u5230\u4e09\u7ea7\u9187\u3002<\/p>\n

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

\u56fe7\uff1aNicolaou\u2018s Synthesis of Aldehyde 32 & Fragment 33<\/em><\/p>\n

\u7ecfPaterson Boron Aldol Reaction<\/em>\u7532\u57fa\u916e33\u4e0e\u919b32\u8fde\u63a5\u5f97\u523031\uff0c\u4f46C-34\u4f4d\u4e0d\u662f\u671f\u671b\u7684\u624b\u6027\u3002Mukaiyama Aldol Reaction<\/em><\/a>\u53ef\u4ee5\u76f4\u63a5\u5f97\u5230\u671f\u671b\u7684\u624b\u6027\uff0c\u4f46\u6240\u6709\u7684\u5c1d\u8bd5\u90fd\u76f4\u63a5\u4f7f32\u5206\u89e3\u3002\u867d\u7136\u4e0d\u662f\u671f\u671b\u7684\u624b\u6027\uff0c\u4f46\u662f\u5728\u540e\u9762\u7684\u53cd\u5e94\u4e2d\uff0c\u6b64\u624b\u6027\u4e2d\u5fc3\u6709\u671b\u53ef\u4ee5\u5f97\u5230\u8f6c\u6362\uff1b31\u7684C-34\u4f4d\u5148\u7528\u82c4\u57fa\u4fdd\u62a4\u540e\uff0cDDQ\u8131\u9664PMB\u4fdd\u62a4\u5f9781\uff1b\u5c0681\u7528\u50ac\u5316\u91cf\u7684PPTS\u50ac\u5316\u5728\u7532\u9187\u4e2d\u53cd\u5e94\u5f97\u7f29\u916e82\uff1b\u53e0\u6c2e\u88abH2<\/sub>\u8fd8\u539f\u6210\u4e00\u7ea7\u80fa\u540e\u7ecf83\uff08Teoc-O-(p<\/em>-NO2<\/sub>C6<\/sub>H4<\/sub>)\uff09\u4fdd\u62a4\u5f97\u5230\u9170\u80fa30\uff1b\u6700\u540e\uff0c\u5728Nd(OTf)3<\/sub>\u7684\u50ac\u5316\u4e0b\u5173\u4e0a\u53e6\u4e00\u4fa7\u7684I\u73af\u5f97\u6df7\u7f29\u916e84\u3002<\/p>\n

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

\u56fe8\uff1aNicolaou\u2018s Synthesis of FHI-Ringsystem 84<\/em><\/p>\n

FHI\u73af\u4f53\u7cfb\u53ea\u5269\u5c06C-34\u4f4d\u7684\u624b\u6027\u8f6c\u5316\u6210\u9700\u8981\u7684\u6784\u578b\u4e86\u3002\u4e3a\u6b64\u9996\u5148\u5c06\u6df7\u7f29\u916e84\u7ecfDIBAL-H\u8131\u9664\u82c4\u57fa\u4fdd\u62a4\u540e\uff0c\u518d\u5c06\u8fd8\u539f\u5f97\u5230\u7684\u7f9f\u57fa\u6c27\u5316\u6210\u7fb0\u57fa\u7684\u523086\uff1b\u518d\u5c06C-34\u4f4d\u7684\u7f9f\u57fa\u6c27\u5316\u6210\u7fb0\u57fa\uff0c\u968f\u540e\u8fd8\u539f\u5f97\u523088\uff0c\u901a\u8fc7\u6c27\u5316-\u8fd8\u539f\u7684\u65b9\u6cd5\uff0cC-34\u4f4d\u7684\u6784\u578b\u5f97\u5230\u7ffb\u8f6c\uff1b88\u7684\u7f9f\u57fa\u5148\u88ab\u4fdd\u62a4\uff0c\u968f\u540e\u4e0ecomins reagent\u53cd\u5e94\u5f97\u78fa\u9178\u76d089\uff0c\u6700\u7ec8\u5c06\u78fa\u9178\u76d0\u8f6c\u5316\u4e3a\u70ef\u57fa\u9521\u8bd5\u524222\u3002<\/p>\n

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

\u56fe9\uff1aNicolaou\u2018s Synthesis of FHI-Ring Vinyl Stannane 84<\/em><\/p>\n

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

\u5982\u4e0b\u56fe\u6240\u793a\uff0c21\u548c22\u901a\u8fc7Stille Coupling<\/em>\u94fe\u63a5\u8d77\u6765\u5f9790\uff0c\u8131\u9664H\u73af\u4e0aO\u7684TES\u4fdd\u62a4\u57fa\u540e\u5f97\u4e09\u918720\uff1b20\u5728NIS\u53caNaHCO3<\/sub>\u7684\u6761\u4ef6\u4e0b\u7acb\u4f53\u9009\u62e9\u6027\u7684\u5f62\u6210G\u73af\uff0cF\u73af\u4e0a\u7684\u7898\u968f\u540e\u7ecf\u81ea\u7531\u57fa\u53cd\u5e94\u8f6c\u6362\u6210H\u5f97\u523093\uff0846\uff09\uff1b\u78b1\u6027\u6761\u4ef6\u4e0b\u8131\u9664A\u73af\u4fa7\u94fe\u4e0a\u7684\u4e59\u9170\u57fa\u5f97\u4e00\u7ea7\u9187\uff0c\u968f\u540e\u53d1\u751f\u4e24\u6b65\u6c27\u5316\u5f97\u7aef\u57fa\u5904\u7fa7\u917895\uff0c\u6700\u540e\u5728TBAF\u6761\u4ef6\u4e0b\u8131\u9664N\u4e0a\u4fdd\u62a4\u57fa\uff0c\u5b8c\u6210azaspiracid-1\u7684\u5168\u5408\u6210\u3002<\/p>\n

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

 <\/p>\n

\u56fe10\uff1aNicolaou\u2018s Total Synthesis of Azaspiracid-1<\/em><\/p>\n

 <\/p>\n

\u53c2\u8003\u6587\u732e<\/strong><\/h4>\n
    \n
  1. (a) K. C. Nicolaou, M. O. Frederick, G. Petrovic, K. P. Cole, E. Z. Loizidou, Angew.<\/em>\u00a0Chem. Int. Ed.<\/em> 2006, 45<\/em>, 2609.DOI: 10.1002\/anie.200600295<\/a> (b) K. C. Nicolaou, M. O. Frederick, E. Z. Loizidou, G. Petrovic, K. P. Cole, T. V. Koftis, Y. M. A. Yamada, Chem. Asian. J. <\/em>2006, 1\u20132<\/em>, 245.DOI: 10.1002\/asia.200600059<\/a>;<\/li>\n
  2. 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
  3. (a) Robert H. Grubbs, Sukbok Chang, Tetrahedron<\/em>, 1998, 54<\/em>, 4413.org\/10.1016\/ S0040-4020(97)10427-6<\/a> (b)A. F\u00fcrstner, Angew. Chem. Int. Ed<\/em>. 2000, 39<\/em>, 3012. DOI: 10.1002\/1521-3773(20000901)39 <\/a>(c) K. C. Nicolaou, P. G. Bulger, D. Sarlah, Angew. Chem. Int. Ed.<\/em> 2005, 44<\/em>, 4490. DOI: 10.1002\/anie.200500369<\/a>;<\/li>\n
  4. Arnab K. Chatterjee, Tae-Lim Choi, Daniel P. Sanders, Robert H. Grubbs, J.<\/em>\u00a0Am. Chem. Soc.,<\/em> 2003, 125<\/em>, 11360. DOI: 10.1021\/ja0214882<\/a>;<\/li>\n
  5. (a)Prabhakar K. Jadhav, Krishna S. Bhat, P. T. Perumal, Herbert C. Brown, J.\u00a0Org. Chem.,<\/em> 1986, 51<\/em>, 432. DOI: 10.1021\/jo00354a003<\/a> (b) Uday S. Racherla, Herbert C. Brown, J. Org. Chem.,<\/em> 1991, 56<\/em>, 401. DOI: 10.1021\/jo00001a072<\/a>;<\/li>\n<\/ol>\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":"\u6295\u7a3f\u4f5c\u8005\u00a0alberto-caeiro \u63a5\u4e0a\u4e00\u7bc7\u800c\u6765\uff0c\u8fd9\u91cc\u5c06\u4e3b\u8981\u4ecb\u7ecd\u4e24\u4f4d\u5316\u5b66\u5bb6\u7684\u5408\u6210\u5de5\u4f5c\u3002\u9996\u5148\u4eceK. C. Nicolaou\u6559\u6388\u57282006\u5e74\u7684\u5168\u5408\u6210\u5de5\u4f5c\u5f00\u59cb\u3002 Nicolaou\u2018s\u7684\u5168\u5408\u6210\u7814\u7a76[1] 1). \u9006\u5408\u6210\u5206\u6790 2006\u5e74\u7684\u5408\u6210\u5de5\u4f5c\u4e3b\u8981\u662f\u5efa\u7acb\u5728\u4e4b\u524d\u7684\u7ed3\u6784\u5206\u6790\u4e2d\u7528\u5230\u7684\u5408\u6210\u7b56\u7565\uff0c\u5e76\u4e14\u5728\u6709\u51c6\u786e\u7ed3\u6784\u7684\u57fa\u7840\u4e0a\uff0c\u8bbe\u8ba1\u4e86\u5982\u56fe1\u6240\u793a\u7684\u6539\u8fdb\u7b56\u7565\u3002\u4e3a\u4e86\u6d88\u9664E\u548cF\u73af\u4e4b\u95f4\u5076\u8054\u65f6\u7684\u4f4d\u963b\u5f71\u54cd\uff0c\u9996\u5148\u901a\u8fc7\u7898\u5316\u6210\u919a\u53cd\u5e94\u5c06G\u73af\u4eceF\u4e0a\u5207\u5272\u51fa\u6765\uff0c\u540e\u7531Still\u5076\u8054\u5373\u53ef\u5c06F\u4e0eE\u73af\u76f8\u8fde\u63a5\u8d77\u6765\uff1bD\u4e0eE\u73af\u90e8\u5206\u53ef\u901a\u8fc7\u4e8c\u5511\u70f7\u5076\u8054\u5b9e\u73b0\u6784\u5efa\uff0c\u5177\u4f53\u5982\u4e0b\u3002 \u56fe1\uff1a Nicolaou\u2018s Retrosynthetic Analysis of Azaspiracid-1 \u56fe2\uff1aNicolaou\u2018s Retrosynthetic Analysis of Fragment24&Vinyl Stannane 22 2). Azaspiracid-1\u7684\u5168\u5408\u6210 A\uff1aABCDE\u73af\u4f53\u7cfb\u7684\u5408\u6210 34\u5148\u4e0e\u78f7\u9178\u76d0\u8d1f\u79bb\u5b50\u53cd\u5e94\u751f\u6210\u78f7\u53f6\u7acb\u5fb7\u7684\u524d\u4f5336\uff0c\u540e\u53d1\u751fHornery-Wadsworth-Emmons\u5076\u8054\uff0c\u751f\u6210E\u578b\u53cc\u952e\uff1b38\u7684\u7fb0\u57fa\u8fd8\u539f\u6210\u7f9f\u57fa\u540e\u5728\u4e59\u9178\u4e2d\u8131\u9664\u7f29\u4e19\u916e\u4fdd\u62a4\uff0c\u8fd8\u539f\u65f6\u7684\u9ad8\u6548\u7acb\u4f53\u9009\u62e9\u6027\u662f\u56e0\u4e3a\u9502\u79bb\u5b50\u7684\u914d\u4f4d\u4f5c\u7528\u598239\u6240\u793a\uff1b40\u53d1\u751f\u7898\u5316\u6210\u919a\u53cd\u5e94\u5f97\u5230D\u73af\uff0c\u7ecf\u8fc741\u7684\u4e2d\u95f4\u72b6\u6001\u5f97\u523042\uff0c\u5728\u4fdd\u62a4\u4e24\u4e2a\u6e38\u79bb\u7684\u7f9f\u57fa\u540e\uff0c\u8fdb\u884c\u4fdd\u62a4\u57fa\u7684\u4ea4\u6362\uff0c\u518d\u7ecf\u8fc7Swern Oxidation\u5373\u53ef\u5f97\u523028\uff0c\u5f53\u7136\uff0c\u5176\u4e2d\u53ef\u4ee5\u4e0d\u9700\u8981\u8fdb\u884c\u4fdd\u62a4\u57fa\u7684\u4ea4\u6362\uff0c\u4f46\u901a\u8fc7\u8fd9\u4e00\u6b65\uff0c\u524d\u4e00\u4ee3\u5408\u6210\u7b56\u7565\u4e2d\u7684\u539f\u6599\u5c31\u53ef\u4ee5\u5728\u6b64\u5f97\u5230\u5229\u7528\u3002 \u56fe3\uff1aNicolaou\u2018s Synthesis of D-ring Aldehyde 28 \u70ef\u4e19\u918747\u5728NCS\u548cMe2S\u4f5c\u7528\u4e0b\u539f\u4f4d\u6c2f\u4ee3\u540e\uff0c\u53d1\u751f\u4e8c\u567b\u70f7\u5076\u8054\u5f97\u523050\uff0c\u518d\u7528\u4e59\u4e8c\u9187\u4fdd\u62a4\u7fb0\u57fa\u5f9751\uff1b51\u5148\u8131TBDPS\u4fdd\u62a4\u540e\u518d\u8fdb\u884c\u7898\u4ee3\u5f9729\uff1b29\u9700\u52a02eq\u7684\u00adt-BuLi\u8131\u9664\u7898\uff0c1\u5f53\u91cf\u7528\u4e8e\u8131\u9664\u7898\uff0c\u53e6\u4e00\u5f53\u91cf\u4f7ft-BuI\u5f62\u6210\u5f02\u4e01\u70ef\u3001\u5f02\u4e01\u70f7\u4e0e\u7898\u5316\u9502\uff0c\u4ece\u800c\u53cd\u5e94\u80fd\u591f\u5411\u53f3\u8fdb\u884c\u5f62\u6210\u8d1f\u79bb\u5b50\uff0c\u540e\u53d1\u751fDess-Martin\u6c27\u5316\u5f97\u523027\uff1b27\u7ecfLewis\u9178\u8bf1\u5bfc\u7684domino\u53cd\u5e94\uff0c\u901a\u8fc7\u8131\u9664TES\u57fa\u56e2\u4e0e\u4e19\u916e\u4fdd\u62a4\u57fa\uff0c\u5f62\u6210ABC\u4e09\u73af\u5f97\u5230\u768426\u5728C-10\u4f4d\u7684\u5dee\u5411\u5f02\u6784\u4f53dr\u503c\u4e3a6\uff1a1[2]\uff1b26\u7aef\u57fa\u5904\u4e00\u7ea7\u9187\u6c27\u5316\u6210\u7fb0\u57fa\u540e\uff0c\u53d1\u751fWittig\u53cd\u5e94\u5f97\u523052\uff1b52\u5728Grubbs\u2161 cat. \u7684\u50ac\u5316\u4e0b\uff0c\u53d1\u751f\u70ef\u70c3\u590d\u5206\u89e3\u53cd\u5e94\u5f97\u5230ABCD\u56db\u73af\u90e8\u520654[3, 4]\u3002 \u56fe4\uff1aNicolaou\u2018s Synthesis of ABCD Ring Systme 54 25\u662f\u6784\u5efaE\u73af\u7684\u4e3b\u8981\u524d\u4f53\u3002\u4ece\u624b\u6027\u73af\u5185\u916f55\u51fa\u53d1\uff0c\u5148\u7ecfDIBAL-H\u8fd8\u539f\u6210\u73af\u534a\u7f29\u919b56\u540e\u5728Lewis\u9178\u50ac\u5316\u4e0b\u5f00\u73af\u5e76\u75281,3-\u4e19\u4e8c\u786b\u9187\u4fdd\u62a4\u919b\u57fa\u5f9757\uff1b\u4e00\u7ea7\u9187\u7ecfDess-Martin\u6c27\u5316\u5f97\u919b58\u540e\uff0c\u4e0e61\u53d1\u751fNozaki-Hiyama-Kishi\u5076\u8054\u5f9762\uff1b62\u5148\u6c27\u5316\u540e\u8fd8\u539f\u5f97\u5230\u9700\u8981\u6784\u8c61\u7684\u7f9f\u57fa64\uff1b64\u5148\u8131TBS\u4fdd\u62a4\u5f97\u52302\u9187\u540e\uff0c\u6362\u4fdd\u62a4\u57fa\u5f97\u523025 \u56fe5\uff1aNicolaou\u2018s Synthesis of Alkyl Iodide 29 54\u8131TBDPS\u4fdd\u62a4\u540e\uff0c\u5148\u540e\u7ecf\u5386Swern\u6c27\u5316\u53caPinnick\u6c27\u5316\u5f97\u5230\u76f8\u5e94\u7684\u7fa7\u9178\u540e\u916f\u5316\u5f9724\uff1b24\u7ecf\u4e8c\u567b\u70f7\u5076\u8054\u5f9723\u540e\uff0cDIBAL-H\u8fd8\u539f\u5f97\u5230\u7684C-20\u4f4d\u76842\u7ea7\u7f9f\u57fa\uff0cTBAF\u8131\u9664\u7f9f\u57fa\u7684\u4fdd\u62a4\u57fa\uff0c\u6700\u7ec8\u5f97\u56db\u9187\u5316\u5408\u726967\uff1b\u7528\u4e59\u9170\u6c2f\u5c06\u7aef\u7f9f\u57fa\u4fdd\u62a4\u540e\uff0c\u6c27\u5316\u6761\u4ef6\u4e0b\u8131\u9664\u4e8c\u786b\u9187\u4fdd\u62a4\u5f97\u5230\u7684\u7fb0\u57fa\u7acb\u523b\u4e0e\u6e38\u79bb\u7684\u7f9f\u57fa\u7f9f\u919b\u7f29\u5408\u5f97\u534a\u7f29\u916e\uff0c\u5b8c\u6210E\u73af\u7684\u6784\u5efa\uff0c\u5f9721\u3002 \u56fe6\uff1aNicolaou\u2018s Synthesis of ABCDE Ring Fragment 21 B\uff1aFHI\u73af\u4f53\u7cfb\u7684\u5408\u6210 FHI\u73af\u4f53\u7cfb\u7684\u5408\u6210\u9996\u5148\u4eceF\u73af\u7684\u6784\u5efa\u5f00\u59cb\u3002L-\u9152\u77f3\u9178\u62c6\u5206\u5f97\u5230\u7684\u4e8c\u918769\u5148\u5355\u4fdd\u62a4\u7f9f\u57fa\uff0cPMP\u4fdd\u62a4\u57fa\u5728\u8fd8\u539f\u6761\u4ef6\u4e0b\u5207\u65ad\u4e00\u4fa7\u7684C-O\u952e\uff0c\u5f97\u5230\u94fe\u72b6\u90bb\u4f4d\u4e8c\u918770\uff0c\u968f\u540e\u88ab\u6c27\u5316\u5f97\u5230\u919b71\uff1b71\u7ecf\u8fc7Brown Allylation\u53cd\u5e94\u540e\u9ad8\u9009\u62e9\u6027\u7684\u5f97\u5230\u9ad8\u70ef\u4e19\u918772[5]\u3002\u6e38\u79bb\u7684\u7f9f\u57fa\u4e0e\u4e19\u70ef\u9178\u53d1\u751f\u916f\u5316\u53cd\u5e94\u5f9774\uff0c\u968f\u540e\u5728Grubbs\u2160\u50ac\u5316\u5242\u4e0b\u8fdb\u884c\u70ef\u70c3\u590d\u5206\u89e3\u53cd\u5e94\u5173\u73af\u5f97\u03b1,\u03b2-\u4e0d\u9971\u548c\u916f75\uff1b\u70f7\u57fa\u94dc\u9502\u8bd5\u5242\u4e0e75\u7ecf\u8fc775\u2018\u6240\u793a\u8fc7\u6e21\u6001\u53d1\u751f1,4-\u5171\u8f6d\u52a0\u6210\u5f97\u5230\u73af\u5185\u916f76\uff0c\u968f\u540e\u5728TBAF\u7684\u4f5c\u7528\u4e0b\u8131\u9664\u4fdd\u62a4\u57fa\u7684\u4e00\u7ea7\u9187\u88ab\u6c27\u5316\u6210\u919b32\u3002 \u788e\u724733\u7684\u5408\u6210\u662f\u4ece\u53cd\u5f0f55\u5f00\u59cb\u7684\u3002ent-55\u5728Lewis\u9178\u4f5c\u7528\u4e0b\u5f00\u73af\u5f97\u5230weinerb\u9170\u80fa77\uff1b77\u4e2d\u7aef\u7f9f\u57fa\u4e0eTsCl\u53cd\u5e94\u540e\uff0c\u88ab\u53e0\u6c2e\u53d6\u4ee3\u5f97\u53e0\u6c2e\u5316\u5408\u726978\uff1b78\u4e0e\u7532\u57fa\u9502\u53d1\u751f\u4eb2\u6838\u53d6\u4ee3\u5f9733\uff0c\u5176\u4e2d\u7531\u4e8e\u9502\u79bb\u5b50\u7684\u914d\u4f4d\u5f62\u6210\u7a33\u5b9a\u7684\u4e2d\u95f4\u4f5379\uff0c\u4f7f\u5f9778\u4e0d\u4f1a\u88ab\u8fd8\u539f\u8fc7\u5ea6\u5f97\u5230\u4e09\u7ea7\u9187\u3002 \u56fe7\uff1aNicolaou\u2018s Synthesis of Aldehyde 32 & Fragment 33 \u7ecfPaterson Boron Aldol Reaction\u7532\u57fa\u916e33\u4e0e\u919b32\u8fde\u63a5\u5f97\u523031\uff0c\u4f46C-34\u4f4d\u4e0d\u662f\u671f\u671b\u7684\u624b\u6027\u3002Mukaiyama Aldol Reaction\u53ef\u4ee5\u76f4\u63a5\u5f97\u5230\u671f\u671b\u7684\u624b\u6027\uff0c\u4f46\u6240\u6709\u7684\u5c1d\u8bd5\u90fd\u76f4\u63a5\u4f7f32\u5206\u89e3\u3002\u867d\u7136\u4e0d\u662f\u671f\u671b\u7684\u624b\u6027\uff0c\u4f46\u662f\u5728\u540e\u9762\u7684\u53cd\u5e94\u4e2d\uff0c\u6b64\u624b\u6027\u4e2d\u5fc3\u6709\u671b\u53ef\u4ee5\u5f97\u5230\u8f6c\u6362\uff1b31\u7684C-34\u4f4d\u5148\u7528\u82c4\u57fa\u4fdd\u62a4\u540e\uff0cDDQ\u8131\u9664PMB\u4fdd\u62a4\u5f9781\uff1b\u5c0681\u7528\u50ac\u5316\u91cf\u7684PPTS\u50ac\u5316\u5728\u7532\u9187\u4e2d\u53cd\u5e94\u5f97\u7f29\u916e82\uff1b\u53e0\u6c2e\u88abH2\u8fd8\u539f\u6210\u4e00\u7ea7\u80fa\u540e\u7ecf83\uff08Teoc-O-(p-NO2C6H4)\uff09\u4fdd\u62a4\u5f97\u5230\u9170\u80fa30\uff1b\u6700\u540e\uff0c\u5728Nd(OTf)3\u7684\u50ac\u5316\u4e0b\u5173\u4e0a\u53e6\u4e00\u4fa7\u7684I\u73af\u5f97\u6df7\u7f29\u916e84\u3002 \u56fe8\uff1aNicolaou\u2018s Synthesis of FHI-Ringsystem 84 FHI\u73af\u4f53\u7cfb\u53ea\u5269\u5c06C-34\u4f4d\u7684\u624b\u6027\u8f6c\u5316\u6210\u9700\u8981\u7684\u6784\u578b\u4e86\u3002\u4e3a\u6b64\u9996\u5148\u5c06\u6df7\u7f29\u916e84\u7ecfDIBAL-H\u8131\u9664\u82c4\u57fa\u4fdd\u62a4\u540e\uff0c\u518d\u5c06\u8fd8\u539f\u5f97\u5230\u7684\u7f9f\u57fa\u6c27\u5316\u6210\u7fb0\u57fa\u7684\u523086\uff1b\u518d\u5c06C-34\u4f4d\u7684\u7f9f\u57fa\u6c27\u5316\u6210\u7fb0\u57fa\uff0c\u968f\u540e\u8fd8\u539f\u5f97\u523088\uff0c\u901a\u8fc7\u6c27\u5316-\u8fd8\u539f\u7684\u65b9\u6cd5\uff0cC-34\u4f4d\u7684\u6784\u578b\u5f97\u5230\u7ffb\u8f6c\uff1b88\u7684\u7f9f\u57fa\u5148\u88ab\u4fdd\u62a4\uff0c\u968f\u540e\u4e0ecomins reagent\u53cd\u5e94\u5f97\u78fa\u9178\u76d089\uff0c\u6700\u7ec8\u5c06\u78fa\u9178\u76d0\u8f6c\u5316\u4e3a\u70ef\u57fa\u9521\u8bd5\u524222\u3002 \u56fe9\uff1aNicolaou\u2018s Synthesis of FHI-Ring Vinyl Stannane 84 C\uff1a\u788e\u7247\u8fde\u63a5\u53ca\u5168\u5408\u6210 \u5982\u4e0b\u56fe\u6240\u793a\uff0c21\u548c22\u901a\u8fc7Stille Coupling\u94fe\u63a5\u8d77\u6765\u5f9790\uff0c\u8131\u9664H\u73af\u4e0aO\u7684TES\u4fdd\u62a4\u57fa\u540e\u5f97\u4e09\u918720\uff1b20\u5728NIS\u53caNaHCO3\u7684\u6761\u4ef6\u4e0b\u7acb\u4f53\u9009\u62e9\u6027\u7684\u5f62\u6210G\u73af\uff0cF\u73af\u4e0a\u7684\u7898\u968f\u540e\u7ecf\u81ea\u7531\u57fa\u53cd\u5e94\u8f6c\u6362\u6210H\u5f97\u523093\uff0846\uff09\uff1b\u78b1\u6027\u6761\u4ef6\u4e0b\u8131\u9664A\u73af\u4fa7\u94fe\u4e0a\u7684\u4e59\u9170\u57fa\u5f97\u4e00\u7ea7\u9187\uff0c\u968f\u540e\u53d1\u751f\u4e24\u6b65\u6c27\u5316\u5f97\u7aef\u57fa\u5904\u7fa7\u917895\uff0c\u6700\u540e\u5728TBAF\u6761\u4ef6\u4e0b\u8131\u9664N\u4e0a\u4fdd\u62a4\u57fa\uff0c\u5b8c\u6210azaspiracid-1\u7684\u5168\u5408\u6210\u3002   \u56fe10\uff1aNicolaou\u2018s Total Synthesis of Azaspiracid-1   \u53c2\u8003\u6587\u732e (a) K. C. Nicolaou, M. O. Frederick, G. 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