{"id":55348,"date":"2025-03-31T08:00:06","date_gmt":"2025-03-31T00:00:06","guid":{"rendered":"\/\/www.gsbet888.com\/?p=55348"},"modified":"2025-03-31T19:43:42","modified_gmt":"2025-03-31T11:43:42","slug":"scabrolide-b-ineleganolide%e4%bb%a5%e5%8f%8a%e7%9b%b8%e5%85%b3norcembranoids%e7%9a%84%e5%85%a8%e5%90%88%e6%88%90","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2025\/03\/scabrolide-b-ineleganolide%e4%bb%a5%e5%8f%8a%e7%9b%b8%e5%85%b3norcembranoids%e7%9a%84%e5%85%a8%e5%90%88%e6%88%90.html","title":{"rendered":"Scabrolide B, Ineleganolide\u4ee5\u53ca\u76f8\u5173Norcembranoids\u7684\u5168\u5408\u6210"},"content":{"rendered":"

\u4f5c\u8005\uff1aSynthetic Pioneer<\/p>\n

\u5bfc\u8bfb<\/strong><\/h4>\n

\u8fd1\u65e5\uff0c\u83b1\u65af\u5927\u5b66\u7684David Sarlah\u56e2\u961f\u5728J. Am. Chem. Soc.\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e86Scabrolide B, Ineleganolide,\u4ee5\u53ca\u76f8\u5173norcembranoids\u7684\u5168\u5408\u6210\u3002Sarlah\u56e2\u961f\u901a\u8fc7\u7247\u6bb5\u5076\u8054\/\u73af\u5408\u7b56\u7565\uff0c\u4ece\u800c\u5b9e\u73b0\u4e86\u5177\u67095\/7\/6 \u73af\u7cfb\u7684norcembranoids\uff08\u5176\u4e2d\u5305\u62ec(+)-ineleganolide\u3001(\u2212)-scabrolide B\u3001(\u2212)-sinuscalide C \u548c (+)-fragilolide A\uff09\u7684\u7b80\u6d01\u5168\u5408\u6210\u3002\u5206\u5b50\u7ed3\u6784\u4e2d\u7684\u6838\u5fc3\u4e03\u5143\u73af\u662f\u901a\u8fc7norcarvone\u548c\u5f15\u5165\u6f5c\u5728\u4eb2\u7535\u5b98\u80fd\u56e2\u7684\u53cc\u73af\u5185\u916f\u901a\u8fc7\u8fde\u7eed\u7684 Mukaiyama-Michael\/ Mukaiyama-Aldol \u53cd\u5e94\u5f62\u6210\u3002\u540e\u7eed\u5f15\u5165\u654f\u611f\u7684\u70ef\u4e8c\u916e\u90e8\u5206\uff0c\u5e76\u4ece\u624b\u6027\u6c60\u884d\u751f\u7684\u70ef\u916e\u4e2d\u4ee5 11 \u6b65\u751f\u6210 (\u2212)-scabrolide B\u3002\u6700\u540e\uff0c\u901a\u8fc7\u4e00\u6b65\u53cd\u5e94\u53ef\u4ee5\u5206\u522b\u83b7\u5f97 (+)-ineleganolide\u3001(\u2212)-sinuscalide C \u548c (+)-fragilolide A\u3002\"\"<\/p>\n

\n

Total Syntheses of Scabrolide B, Ineleganolide, and Related Norcembranoids<\/p>\n

E. J. Simmons, D. B. Ryffel, D. A. Lopez, Y. D. Boyko, D. Sarlah*<\/p>\n

J. Am. Chem. Soc.<\/em> 2025, 147, 1, 130\u2013135. doi:10.1021\/jacs.4c16629.<\/p><\/blockquote>\n

\u6b63\u6587<\/strong><\/h4>\n

Norcembranoid \u7c7b\u4e8c\u841c\u662f\u4e00\u7c7b\u4ece\u8f6f\u73ca\u745aSinularia\u4e2d\u5206\u79bb\u51fa\u7684\u6d77\u6d0b\u5929\u7136\u4ea7\u7269\uff0c\u5176\u7279\u5f81\u5728\u4e8e\u5177\u6709\u7b3c\u72b6\u3001\u591a\u73af\u7ed3\u6784\uff0c\u5e76\u5c55\u793a\u51fa\u591a\u6837\u5316\u7684\u6c27\u5316\u6001\uff08Figure 1a\uff09\u3002\u8fd9\u4e00\u7c7b\u5929\u7136\u4ea7\u7269\u5305\u542b\u591a\u79cd\u4e0d\u540c\u7684\u9aa8\u67b6\u7c7b\u578b\uff0c\u4f8b\u59825\/7\/6\u548c5\/6\/7\u78b3\u4e09\u73af\u4f53\u7cfb\uff0c\u4ee3\u8868\u6027\u5316\u5408\u7269\u5305\u62ecineleganolide\uff081\uff09\uff0c scabrolide B\uff082\uff09\uff0c sinuscalide C\uff083\uff09\uff0cfragilolide A\uff084\uff09\uff0c \u4ee5\u53cascabrolide A\uff085\uff09 \u548cyonarolide\uff086\uff09\u3002 \u4e00\u4e9bnorcembranoids\u88ab\u62a5\u9053\u5177\u6709\u6297\u767d\u8840\u75c5\u3001\u6297\u8840\u6813\u548c\u6297\u708e\u6d3b\u6027\uff1b\u7136\u800c\uff0c\u7531\u4e8e\u5206\u79bb\u4ea7\u7387\u4f4e\u4ee5\u53ca\u7f3a\u4e4f\u5bf9\u8fd9\u4e9b\u5929\u7136\u4ea7\u7269\u591a\u6837\u6027\u5408\u6210\u7684\u624b\u6bb5\uff0c\u5bf9\u5176\u751f\u7269\u6d3b\u6027\u53ca\u5176\u4e0e\u6838\u5fc3\u7ed3\u6784\u7684\u5173\u7cfb\u7684\u8fdb\u4e00\u6b65\u7814\u7a76\u53d7\u5230\u9650\u5236\u3002\u5c3d\u7ba1\u5982\u6b64\uff0c\u5728\u8fc7\u53bb\u4e09\u5341\u5e74\u4e2d\uff0c\u79d1\u5b66\u754c\u9010\u6e10\u7a81\u7834\u4e86norcembranoids\u7684\u7814\u7a76\u74f6\u9888\uff0c\u5e76\u63ed\u793a\u4e86\u4e0d\u540c\u540c\u7cfb\u7269\u4e4b\u95f4\u7684\u751f\u7269\u5408\u6210\u5173\u7cfb\u3002\u540c\u6837\uff0c\u7531\u4e8e\u5176\u590d\u6742\u7684\u7ed3\u6784\u53ca\u5176\u5728\u8fdb\u4e00\u6b65\u751f\u7269\u5b66\u7814\u7a76\u4e2d\u7684\u6f5c\u5728\u5e94\u7528\u4ef7\u503c\uff0c\u8fd9\u7c7b\u5929\u7136\u4ea7\u7269\u4e5f\u5f15\u8d77\u4e86\u5408\u6210\u5316\u5b66\u754c\u7684\u6781\u5927\u5173\u6ce8\u3002<\/p>\n

Ineleganolide\uff081\uff09\u88ab\u8ba4\u4e3a\u662fnorcembranoid\u5bb6\u65cf\u7684\u6807\u5fd7\u6027\u6210\u5458\uff0c\u5177\u6709\u590d\u6742\u7684\u676f\u72b6\u4e94\u73af\u9aa8\u67b6\uff0c\u5176\u4e2d\u5305\u542b\u4e5d\u4e2a\u7acb\u4f53\u4e2d\u5fc3\uff08\u516b\u4e2a\u662f\u8fde\u7eed\u7684\uff09\u4ee5\u53ca\u4e00\u4e2a\u9ad8\u5ea6\u53d6\u4ee3\u7684\u4e03\u5143\u73af\u3002\u9488\u5bf9ineleganolide\u7684\u5408\u6210\u7814\u7a76\u5df2\u6709\u591a\u9879\u5de5\u4f5c\u5c55\u5f00\uff0c\u5305\u62ecPattenden\u7684\u4eff\u751f\u534a\u5408\u6210[1]<\/sup>\u3002 \u8fd1\u671f\uff0cWood\u56e2\u961f \u3001Stoltz \u56e2\u961f\u548cF\u00fcrstner\u56e2\u961f\u5206\u522b\u5b8c\u6210\u4e86Ineleganolide\uff081\uff09\u7684\u5168\u5408\u6210[2]<\/sup>\u3002\u6b64\u5916\uff0cF\u00fcrstner\u56e2\u961f\u901a\u8fc7\u5bf9scabrolide B\uff082\uff09\u540d\u4e49\u7ed3\u6784\u7684\u5408\u6210\uff0c\u4fc3\u4f7f\u8be5\u5316\u5408\u7269\u7684\u7ed3\u6784\u5f97\u5230\u4e86\u91cd\u65b0\u4fee\u8ba2\u3002\u591a\u4f4d\u5206\u79bb\u5316\u5b66\u5bb6\u4e5f\u901a\u8fc7\u5bf9\u91cd\u65b0\u5206\u79bb\u6837\u54c1\u7684\u8c03\u67e5\uff0c\u8fdb\u4e00\u6b65\u786e\u8ba4\u5e76\u66f4\u6b63\u4e86scabrolide B\u7684\u7ed3\u6784\u3002\u5c3d\u7ba1\u8be5\u5316\u5408\u7269\u66fe\u4ee5sinuscalide D\u7684\u540d\u79f0\u53d1\u8868\u8fc7\uff0c\u4f46\u540e\u6765\u53d1\u73b0\u5176\u5149\u8c31\u7279\u6027\u4e0e\u539f\u59cb\u548c\u91cd\u65b0\u5206\u79bb\u7684scabrolide B\u5b8c\u5168\u76f8\u540c\u3002\u968f\u540e\uff0c\u5728 F\u00fcrstner\u56e2\u961f\u53d1\u8868\u5176\u9488\u5bf9\u5316\u5408\u72692\u7684\u5408\u6210\u7b56\u7565\u4e4b\u540e\uff0c\u4e5f\u8fdb\u4e00\u6b65\u786e\u8ba4\u4e86\u8fd9\u4e00\u7ed3\u6784\u66f4\u6b63\u3002\"\"<\/p>\n

Sarlah\u56e2\u961f\u51c6\u5907\u8bbe\u8ba1\u4e00\u6761\u9ad8\u6548\u7684\u5408\u6210\u8def\u7ebf\uff0c\u9996\u5148\u5b8c\u6210scabrolide B\uff082\uff09\uff0c\u968f\u540e\u5c06scabrolide B\uff082\uff09\u8f6c\u5316\u4e3aineleganolide\uff081\uff09\u3001sinuscalide C\uff083\uff09\u548cfragilolide A\uff084\uff09\u3002\u7531\u4e8e\u4ed6\u4eec\u56e2\u961f\u4e4b\u524d\u5df2\u7ecf\u62a5\u9053\u4e86norcembranoids\u7c7b(\u2212)-scabrolide A\uff085\uff09\u548cyonarolide\uff086\uff09\u7684\u5168\u5408\u6210\uff0c\u8fd9\u4e24\u79cd\u5316\u5408\u7269\u5747\u5177\u67095\/6\/7\u78b3\u73af\u6838\u5fc3\u7ed3\u6784\uff08Figure 1a\uff09[3]<\/sup>\u3002 \u57fa\u4e8e\u4e4b\u524d\u7684\u5de5\u4f5c\uff0c\u4ed6\u4eec\u8ba4\u4e3aineleganolide\uff081\uff09\u53ef\u4ee5\u901a\u8fc7C12 \u5185\u916f\u03b1\u4f4d\u8d28\u5b50\u7684\u5dee\u5411\u5f02\u6784\u5316\u4ee5\u53ca\u5206\u5b50\u5185\u7684\u6c27\u6742Michael\u52a0\u6210\u53cd\u5e94\u4ecescabrolide B\uff082\uff09\u5728\u540e\u671f\u8f6c\u5316\u5f97\u5230\uff08(Figure 1b\uff09\u3002\u800cscabrolide B\uff082\uff09\u7684\u5408\u6210\u53ef\u4ee5\u7531\uff08R\uff09-norcarvone\uff087\uff09\u4e0e\u7f29\u919b\u5185\u916f8\u4e24\u4e2a\u7247\u6bb5\u8fde\u63a5\u4ee5\u53ca\u73af\u5316\u5f97\u5230\u3002\u4ed6\u4eec\u5e0c\u671b\u53ef\u4ee5\u901a\u8fc7\u8fde\u7eed\u7684Mukaiyama-Michael\u52a0\u6210\u53cd\u5e94\u548cMukaiyama-Aldol\u53cd\u5e94\u6765\u6784\u5efa\u5177\u6709\u6311\u6218\u6027\u7684C12\u2013C13\u5e76\u5f62\u6210\u4e03\u5143\u73af\u3002\u6700\u540e\uff0c\u6240\u9700\u7684\u53cc\u73af\u7f29\u919b8\u53ef\u4ee5\u901a\u8fc7Maimone\u56e2\u961f\u53d1\u5c55\u7684\u70ef\u916e\uff0810\uff09 \u548c\u4e9a\u7532\u57fa\u73af\u4e19\u70f7\uff089\uff09\u5728\u954d\u50ac\u5316\u4e0b\u7684[3 + 2] \u73af\u5316\u53cd\u5e94\u5236\u5907\u3002<\/p>\n

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\u4e3a\u4e86\u5b9e\u73b0\u9884\u671f\u7684 Mukaiyama-Aldol\u73af\u5316\u53cd\u5e94\uff0c\u4f5c\u8005\u8ba4\u4e3a\u4e8c\u7532\u57fa\u7f29\u919b\u53ef\u4ee5\u540c\u65f6\u53d1\u6325\u53cc\u91cd\u4f5c\u7528\uff1a\u65e2\u4f5c\u4e3a\u919b\u7684\u4fdd\u62a4\u57fa\uff0c\u53c8\u4f5c\u4e3a\u4e00\u79cd\u9690\u853d\u7684\u4eb2\u7535\u8bd5\u5242\uff0c\u5373\u80fd\u591f\u5728\u540e\u7eed\u7684\u73af\u5316\u6b65\u9aa4\u4e2d\u901a\u8fc7\u9002\u5f53\u7684\u8def\u6613\u65af\u9178\u6fc0\u6d3b\u6765\u4f5c\u4e3a\u4e00\u79cd\u6d3b\u6027\u7684\u4eb2\u7535\u8bd5\u5242\u3002\u4e3a\u4e86\u83b7\u5f97\u76ee\u6807\u7f29\u919b8\uff0c\u4f5c\u8005\u9996\u5148\u5c06\u919b 14 \u4e0eWittig\u8bd5\u524215\u53cd\u5e94\uff0c\u968f\u540e\u7528\u65e0\u6c34\u7684\u76d0\u9178\u7532\u9187\u6eb6\u6db2\u6765\u5904\u7406\u8be5\u4ea7\u7269\u3002\u8fd9\u4e00\u8fc7\u7a0b\u4fc3\u8fdb\u4e86Wittig\u53cd\u5e94\u4ea7\u7269\u7532\u57fa\u4e59\u70ef\u57fa\u919a\u5b8c\u5168\u8f6c\u5316\u4e3a\u7f29\u919b 8\u3002\"\"<\/p>\n

\u968f\u540e\uff0c\u57fa\u4e8eVanderwal \u56e2\u961f\u7684\u7ed3\u679c\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5185\u916f 8\u901a\u8fc7\u6e29\u548c\u7684\u70ef\u9187\u5316\u53cd\u5e94\u6761\u4ef6\u539f\u4f4d\u751f\u6210\u70ef\u9187\u7845\u919a\uff0c\u7136\u540e\u52a0\u5165\u50ac\u5316\u91cf\u7684La(OTf)\u2083\u548c (R)- norcarvone 7\uff0c\u53ef\u4ee5\u5f97\u5230\u5355\u4e00\u7684\u975e\u5bf9\u6620\u4f53\u70ef\u9187\u7845\u919a16\u3002\u5176\u4e2d\u7531\u5185\u916f8\u539f\u4f4d\u751f\u6210\u7684\u70ef\u9187\u7845\u919a\u4ece\u5f02\u4e19\u70ef\u57fa\u7684\u53e6\u4e00\u4fa7\u8fdb\u653b\uff0c\u800c 7 \u5219\u4ece\u53cc\u73af\u7ed3\u6784\u7684\u51f8\u9762\u9760\u8fd1\uff0c\u4ece\u800c\u786e\u7acb\u4e86 C12 \u548c C13 \u7684\u6240\u9700\u7acb\u4f53\u5316\u5b66\u3002\u7cbe\u786e\u63a7\u5236\u73af\u5316\u6b65\u9aa4\u5bf9\u4e8e\u5206\u5b50\u7684\u5408\u6210\u81f3\u5173\u91cd\u8981\uff0c\u4f5c\u8005\u65e9\u671f\u7684\u7b56\u7565\u662f\u901a\u8fc7\u5206\u5b50\u5185\u7684\u6210\u73af\u53cd\u5e94\u6765\u5f62\u6210 C12\u2212C13 \u952e\uff0c\u4f46\u90fd\u6ca1\u6709\u5f97\u5230\u6b63\u786e\u7684\u7acb\u4f53\u5316\u5b66\u3002\"\"<\/p>\n

\"\"\u5728\u5b8c\u6210\u7247\u6bb5\u5076\u8054\u540e\uff0c\u4f5c\u8005\u5bf9\u4e8e\u5173\u952e\u7684Mukaiyama-Aldol\u73af\u5316\u53cd\u5e94\u8fdb\u884c\u4e86\u7814\u7a76\u3002\u8fd9\u4e00\u8f6c\u5316\u8fc7\u7a0b\u9887\u5177\u6311\u6218\u6027\uff0c\u4f7f\u7528\u591a\u79cd\u8def\u6613\u65af\u9178\uff08\u5982 SnCl\u2084\u3001TiCl\u2084\u3001TMSOTf\u3001BF\u2083\u00b7Et\u2082O \u548c Sc(OTf)\u2083\uff09\u4ec5\u751f\u6210\u4e86\u6c34\u89e3\u526f\u4ea7\u7269\u3002\u968f\u540e\u4f5c\u8005\u53d1\u73b0\uff0c\u5728\u221278 \u00b0C\u4e0b\u4f7f\u7528\u5316\u5b66\u8ba1\u91cf\u7684 Bu\u2082BOTf \u5904\u7406 16\uff0c\u53ef\u4ee5\u5feb\u901f\u5f62\u6210\u4e03\u5143\u73af\u7ed3\u6784\uff0c\u5e76\u901a\u8fc7\u4e59\u9178\u4fc3\u8fdb\u7684 \u03b2-\u6d88\u9664\u53ef\u4ee5\u751f\u6210\u70ef\u916e 17\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0cBu\u2082BOTf \u662f\u552f\u4e00\u80fd\u591f\u5b8c\u6210\u8fd9\u4e00\u8f6c\u5316\u7684\u8bd5\u5242\uff0c\u4e5f\u662f\u9996\u6b21\u5728\u70ef\u9187\u7845\u919a\u4e0e\u7f29\u919b\u7684Mukaiyama-Aldol\u53cd\u5e94\u4e2d\u4f7f\u7528 Bu\u2082BOTf\u3002\u867d\u7136\u6709\u4e00\u4f8b\u76f8\u5173\u8bd5\u5242\uff089BBN\u2212OTf\uff09\u5728\u5206\u5b50\u95f4\u7684\u53cd\u5e94\u4e2d\u88ab\u4f7f\u7528[5]<\/sup>\u3002\u4f5c\u8005\u63a8\u6d4b\uff0c\u70ef\u9187\u7845\u919a16\u53ef\u80fd\u4f1a\u5feb\u901f\u4e0e Bu\u2082BOTf \u53d1\u751f\u4ea4\u6362\uff0c\u751f\u6210\u70ef\u9187\u787c\u5316\u7269\uff0c\u4ece\u800c\u8fc5\u901f\u5b9e\u73b0\u5bf9\u540c\u65f6\u751f\u6210\u7684\u6c27\u9393\u79bb\u5b50\u7684\u6355\u83b7\u3002<\/p>\n

\u5728\u6210\u529f\u6784\u5efa\u5b8c\u6574\u7684 5\/7\/6 \u78b3\u73af\u9aa8\u67b6\u540e\uff0c\u5b8c\u6210 scabrolide B (2) \u7684\u6700\u540e\u4e00\u6b65\u662f\u5177\u6709\u6311\u6218\u6027\u7684 \u03b3-\u4f4d\u70b9\u6c27\u5316\u3002\u76f4\u63a5\u7684\u70ef\u4e19\u4f4d\u6c27\u5316\u5e76\u672a\u5f97\u5230\u9700\u8981\u7684\u4ea7\u7269\u3002\u968f\u540e\u4f5c\u8005\u5229\u7528\u4e4b\u524d\u4f7f\u7528\u7684\u9700\u6c27\u6c27\u5316\u6761\u4ef6\uff08DBU \u548c\u4e09\u7532\u57fa\u4e9a\u78f7\u9178\u916f\uff09\u4ee5\u8f83\u9ad8\u7684\u6536\u7387\u751f\u6210 \u03b1-\u7f9f\u57fa\u916e18\u3002\u968f\u540e\u7528 TASF \u548c\u6c34\u5728 80\u00b0C \u4e0b\u5904\u740618\uff0c\u53ef\u53bb\u9664\u7845\u57fa\u4fdd\u62a4\u57fa\uff0c\u5f97\u5230\u4e09\u7ea7\u9187 19\u3002\u901a\u8fc7\u5355\u6676 X \u5c04\u7ebf\u884d\u5c04\u5206\u6790\u9a8c\u8bc1\u4e86\u5316\u5408\u7269 19 \u5728 C12 \u548c C13 \u4f4d\u7684\u7acb\u4f53\u5316\u5b66\uff0c\u4ee5\u53ca\u65b0\u751f\u6210\u7684\u4e09\u7ea7\u9187\u7684\u7acb\u4f53\u5316\u5b66\u3002\u7136\u800c\uff0c\u901a\u8fc7\u6c27\u5316\u6216\u6c27\u5316\u8fd8\u539f\u4e2d\u6027\u7684\u8f6c\u4f4d\u7b56\u7565\u5c06\u918719\u8f6c\u5316\u4e3a \u03b3-\u4f4d\u6c27\u5316\u4ea7\u7269\u5747\u672a\u594f\u6548\u3002\u4f5c\u8005\u91c7\u7528\u4e4b\u524d\u4f7f\u7528\u7684\u6c27\u5316\u8f6c\u4f4d\u65b9\u6cd5\uff0c\u4ec5\u80fd\u56de\u6536\u8d77\u59cb\u6750\u6599\u6216\u5728\u5ef6\u957f\u53cd\u5e94\u65f6\u95f4\u540e\u5bfc\u81f4\u5206\u89e3\u3002\u968f\u540e\u4f5c\u8005\u53d1\u73b0\u7528 SmI\u2082 \u8fd8\u539f 19 \u4f1a\u5f15\u53d1\u4e09\u7ea7\u7f9f\u57fa\u7684 \u03b1-\u6d88\u9664\uff0c\u800c\u751f\u6210\u7684\u4e8c\u70ef\u9187\u9490\u76d0\u53ef\u4ee5\u76f4\u63a5\u4e0e O\u2082 \u53cd\u5e94\uff0c\u5f97\u5230\u5f62\u5f0f\u4e0a\u7684\u8f6c\u4f4d\u4ea7\u7269 20\u3002\u5728\u5b9e\u9a8c\u4e2d\uff0c\u4f5c\u8005\u8fd8\u68c0\u6d4b\u5230\u4e86\u5fae\u91cf\u7684 scabrolide B (2)\uff0c\u53ef\u80fd\u662f\u901a\u8fc7\u8fc7\u6c27\u81ea\u7531\u57fa\u88c2\u89e3\u751f\u6210\u3002\u4ee5\u9ad8\u6536\u7387\u548c\u53ef\u91cd\u590d\u6027\u65b9\u5f0f\u5b9e\u73b0\u8fd9\u79cd\u88c2\u89e3\u4ee5\u76f4\u63a5\u5f97\u5230 2 \u7684\u5c1d\u8bd5\u5747\u672a\u6210\u529f\u3002\u7814\u7a76\u4e2d\u4f5c\u8005\u8fd8\u53d1\u73b0\uff0c\u7528\u5206\u5b50\u6c27\u6c27\u5316 Sm(III) \u70ef\u9187\u76d0\u7684\u53cd\u5e94\u901f\u5ea6\u8f83\u6162\u3002\u5c06\u4e8c\u70ef\u9187\u9490\u76d0\u66b4\u9732\u5728\u6c27\u6c14\u73af\u5883\u4e2d12 \u5c0f\u65f6\u540e\u53ef\u4ee5\u5f62\u6210\u9187 20\uff0c\u540c\u65f6\u5728\u53cd\u5e94\u540e\u5904\u7406\u540e\u5e76\u672a\u68c0\u6d4b\u5230\u8d28\u5b50\u5316\u6216\u8131\u6c27\u7684\u526f\u4ea7\u7269\u3002\u4f5c\u8005\u63a8\u6d4b\uff0c\u5728\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u8fc7\u6c27\u5316\u7269\u88ab\u8fc5\u901f\u8fd8\u539f\uff0c\u8fc7\u6c27\u5316\u7269\u4e2d\u95f4\u4f53\u672a\u79ef\u7d2f\uff0c\u56e0\u6b64\u65e0\u6cd5\u8fdb\u4e00\u6b65\u64cd\u63a7\u5176\u5411\u88c2\u89e3\u65b9\u5411\u8f6c\u5316\u3002\u7c7b\u4f3c\u7684\u53cd\u5e94\u5728\u5176\u4ed6\u4f53\u7cfb\u4e2d\u4e5f\u6709\u5148\u4f8b\uff0c\u5176\u4e2d Sm(III) \u70ef\u9187\u76d0\u4e0e\u6c27\u6c14\u53cd\u5e94\u751f\u6210\u9187\uff0c\u5373\u4f7f\u6ca1\u6709\u989d\u5916\u7684\u8fd8\u539f\u5242\u3002\u8fd9\u79cd O\u2212O \u952e\u88c2\u89e3\u5728\u5f62\u5f0f\u4e0a\u8868\u73b0\u4e3a\u6c27\u5316\u6761\u4ef6\u4e0b\u7684\u8fd8\u539f\u884c\u4e3a\uff0c\u5c3d\u7ba1\u5176\u786e\u5207\u673a\u5236\u5c1a\u4e0d\u660e\u786e\uff0c\u4f46\u5df2\u6709\u591a\u79cd\u53cd\u5e94\u8def\u5f84\u88ab\u63d0\u51fa\u6765\u89e3\u91ca\u8fd9\u4e00\u73b0\u8c61[6]<\/sup>\u3002\u5c3d\u7ba1\u5982\u6b64\uff0c\u4f5c\u8005\u80fd\u591f\u5e72\u51c0\u5730\u5b8c\u6210\u8fd9\u4e00\u5f62\u5f0f\u4e0a\u4fdd\u6301\u6c27\u5316\u8fd8\u539f\u4e2d\u6027\u7684\u8f6c\u4f4d\u53cd\u5e94\uff0c\u751f\u6210 20\u3002\u968f\u540e\uff0c\u5229\u7528 Dess-Martin \u8bd5\u5242 (DMP) \u5bf9 \u03b3-\u4f4d\u7f9f\u57fa\u8fdb\u884c\u6c27\u5316\uff0c\u987a\u5229\u5f97\u5230\u4e86 (\u2212)-scabrolide B (2)\u3002\u8be5\u8def\u7ebf\u4ece\u70ef\u916e 10 \u51fa\u53d1\uff0c\u4ec5\u9700 11 \u6b65\uff0c\u6574\u4f53\u6536\u7387\u4e3a 4.0%\u3002\u6b64\u5916\uff0c\u8fd9\u4e00\u65b9\u6cd5\u53ef\u4ee5\u653e\u5927\u89c4\u6a21\uff0c\u603b\u5171\u5236\u5907\u4e86\u8d85\u8fc7 80 mg \u7684(\u2212)-scabrolide B (2)\u3002<\/p>\n

\u5728\u83b7\u5f97\u5145\u8db3\u7684 (\u2212)-scabrolide B (2) \u540e\uff0c\u4f5c\u8005\u63a2\u7d22\u4e86\u5176\u8f6c\u5316\u4e3a (+)-ineleganolide (1) \u7684\u8fc7\u7a0b \uff08Scheme 2\uff09\u3002F\u00fcrstner \u56e2\u961f\u7684\u7814\u7a76\u8868\u660e\uff0c\u5c06 scabrolide B (2) \u66b4\u9732\u4e8e\u5f31\u78b1\u6027 Et\u2083N \u5e76\u52a0\u70ed\u53ef\u5b9e\u73b0\u5411 ineleganolide (1) \u7684\u8f6c\u5316\uff0c\u4f46\u8fd9\u4e9b\u6761\u4ef6\u540c\u65f6\u4f1a\u5bfc\u81f4 1 \u7684\u8fdb\u4e00\u6b65\u53cd\u5e94\uff0c\u4ece\u800c\u6536\u7387\u8f83\u4f4e\u3002\u4f5c\u8005\u53d1\u73b0\uff0c\u5728 0\u00b0C \u4e0b\u4f7f\u7528 DBU \u548c MeCN\uff0c\u53ef\u4ee5\u5e72\u51c0\u5730\u5b8c\u6210\u4ece 2 \u5230 ineleganolide (1)\u7684\u8f6c\u5316\uff0c\u5176\u4ea7\u7387\u8fbe\u5230\u4e86 80%\uff08\u4ece 10 \u51fa\u53d1\u7684\u6574\u4f53\u6536\u7387\u4e3a 3.20%\uff0c\u6700\u957f\u7ebf\u6027\u6b65\u9aa4\u4e3a12 \u6b65\uff09\u3002\u8fd9\u4e00\u5355\u6b65\u64cd\u4f5c\u5b9e\u73b0\u4e86 C12 \u4f4d\u7684\u5dee\u5411\u5f02\u6784\u5316\u548c oxa-Michael \u52a0\u6210\u53cd\u5e94\u5f62\u6210\u56db\u6c22\u544b\u5583\u73af\u3002\u4f5c\u8005\u5728\u8be5\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u672a\u68c0\u6d4b\u5230\u8fdb\u4e00\u6b65\u7684\u91cd\u6392\u4ea7\u7269\uff0c\u4e14 2 \u5411 1 \u7684\u8f6c\u5316\u4e0d\u53ef\u9006\u3002\u6b64\u5916\uff0cTBS \u4fdd\u62a4\u7684(\u2212)-scabrolide B\u5728\u76f8\u540c\u6761\u4ef6\u4e0b\u4e0d\u4f1a\u53d1\u751f\u5dee\u5411\u5f02\u6784\u5316\uff0c\u4e5f\u4e0d\u4f1a\u53d1\u751f\u5728\u6ca1\u6709\u70ef\u4e8c\u916e\u6c27\u5316\u6001\u7684\u4e2d\u95f4\u4f53\u4e2d\u3002\u8fd9\u8868\u660e\uff0coxa-Michael \u53ef\u80fd\u5148\u4e8e\u5dee\u5411\u5f02\u6784\u5316\u53d1\u751f\uff0cC12 \u4f4d\u7684\u5dee\u5411\u5f02\u6784\u5316\u66f4\u53ef\u80fd\u901a\u8fc7retro-Michael\/ Michael \u673a\u5236\u800c\u975e\u7b80\u5355\u7684\u53bb\u8d28\u5b50\u5316\/\u8d28\u5b50\u5316\u8fc7\u7a0b\u8fdb\u884c\u3002\"\"<\/p>\n

\u6700\u540e\uff0c(\u2212)-scabrolide B (2) \u8fd8\u53ef\u4ee5\u8fdb\u4e00\u6b65\u8f6c\u5316\u4e3a\u51e0\u79cd\u5176\u4ed6 ineleganane \u7c7b\u5929\u7136\u4ea7\u7269\uff0c\u5305\u62ec (\u2212)-sinuscalide C (3) \u548c (+)-fragilolide A (4)\u3002\u901a\u8fc7 Burgess \u8bd5\u5242\u5bf9\u4e09\u7ea7\u9187\u8fdb\u884c\u8131\u6c34\u53cd\u5e94\uff0c\u751f\u6210\u4e86 (\u2212)-sinuscalide C (3)\uff0c\u8fd9\u4e00\u8f6c\u5316\u6b64\u524d\u5df2\u7531 F\u00fcrstner \u548c\u5176\u4ed6\u7814\u7a76\u8005\u5728\u7c7b\u4f3c\u4f53\u7cfb\u4e2d\u62a5\u9053\u3002 \u53e6\u4e00\u65b9\u9762\uff0c (+)-fragilolide A (4)\u5219\u662f\u901a\u8fc7\u9009\u62e9\u6027 Luche \u8fd8\u539f C3 \u4f4d\u7684\u916e\u6765\u5b9e\u73b0\u5176\u9996\u6b21\u5168\u5408\u6210\u3002\u7531\u4e8e C3 \u4f4d\u7684\u916e\u8f83\u5c11\u53d7\u4f4d\u963b\u5f71\u54cd\uff0c\u6765\u81ea\u51f8\u9762\u7684\u8fd8\u539f\u66f4\u4e3a\u5bb9\u6613\u3002\u5173\u952e\u7684 NOE \u4fe1\u53f7\u8868\u660e C3 \u4f4d\u8d28\u5b50\u4e0e C13 \u4ee5\u53ca\u5f02\u4e19\u70ef\u57fa\u4e9a\u7532\u57fa\u4e4b\u95f4\u5b58\u5728\u7a7a\u95f4\u5173\u8054\uff0c\u8fd9\u8868\u660e\u8fd8\u539f\u662f\u4ece\u5316\u5408\u7269 2 \u7684\u5e95\u9762\u53d1\u751f\uff0c\u8fd9\u4e00\u7ed3\u679c\u4e0e\u6700\u521d\u5206\u79bb\u51fa\u7684\u5929\u7136\u4ea7\u7269\u7684\u5149\u8c31\u6570\u636e\u4e00\u81f4\u3002<\/p>\n

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

Sarlah\u56e2\u961f\u6210\u529f\u5730\u5b8c\u6210\u4e86\u56db\u79cd ineleganane \u7c7b\u4e8c\u841c\u5316\u5408\u7269\u7684\u5408\u6210\uff0c\u5373 (+)-ineleganolide (1)\u3001(\u2212)-scabrolide B (2)\u3001(\u2212)-sinuscalide C (3) \u548c (+)-fragilolide A (4)\uff0c\u8fd9\u4e9b\u5929\u7136\u4ea7\u7269\u5747\u901a\u8fc7 11 \u6216 12 \u6b65\u53cd\u5e94\u4ece\u70ef\u916e 10 \u5236\u5907\u800c\u5f97\u3002\u5176\u5408\u6210\u7b56\u7565\u5177\u6709\u4ee5\u4e0b\u663e\u8457\u7279\u70b9\uff1a<\/p>\n

1\u4e9a\u7532\u57fa\u73af\u4e19\u70f7[3+2]\u73af\u5316\u53cd\u5e94\uff1a\u8fd9\u4e00\u7b56\u7565\u5b9e\u73b0\u4e86\u5feb\u901f\u4e14\u53ef\u63a7\u5730\u83b7\u5f97\u9ad8\u5ea6\u5b98\u80fd\u56e2\u4fee\u9970\u7684\u53cc\u73af\u7247\u6bb5 8\u3002<\/p>\n

2\u5173\u952e\u7684Mukaiyama-Michael\u548cMukaiyama-Aldol\u53cd\u5e94\uff1a\u7f29\u919b8\u4e0e(R)- norcarvone 7\u7684\u53cd\u5e94\u9ad8\u6548\u5730\u6784\u5efa\u4e86\u6838\u5fc3\u4e03\u5143\u73af\uff0c\u800c Bu\u2082BOTf \u5728\u6b64\u7c7b\u5177\u6709\u6311\u6218\u6027\u7684\u73af\u5316\u7b56\u7565\u4e2d\u7684\u72ec\u7279\u4f5c\u7528\u53ef\u80fd\u5177\u6709\u5e7f\u6cdb\u7684\u5e94\u7528\u4ef7\u503c\u3002<\/p>\n

3\u751f\u7269\u9057\u4f20\u8054\u7cfb\uff1a\u901a\u8fc7\u4e0d\u53ef\u9006\u4e14\u5b8c\u5168\u7684\u8f6c\u5316\uff0c\u5c06 (\u2212)-scabrolide B (2) \u8f6c\u5316\u4e3a (+)-ineleganolide (1)\uff0c\u5c55\u793a\u4e86\u8fd9\u4e24\u79cd\u4ee3\u8c22\u4ea7\u7269\u4e4b\u95f4\u53ef\u80fd\u7684\u751f\u7269\u9057\u4f20\u8054\u7cfb\u3002<\/p>\n

4\u8fdb\u4e00\u6b65\u8f6c\u5316\uff1a\u901a\u8fc7\u8131\u6c34\u6216\u9009\u62e9\u6027\u8fd8\u539f\uff0c(\u2212)-scabrolide B (2) \u8fd8\u53ef\u4ee5\u8f6c\u5316\u4e3a (\u2212)-sinuscalide C (3) \u548c (+)-fragilolide A (4)\u3002<\/p>\n

\u53c2\u8003\u6587\u732e<\/strong><\/h4>\n