{"id":39875,"date":"2021-09-01T08:00:02","date_gmt":"2021-09-01T00:00:02","guid":{"rendered":"\/\/www.gsbet888.com\/?p=39875"},"modified":"2021-08-28T15:37:29","modified_gmt":"2021-08-28T07:37:29","slug":"%e8%a5%bf%e5%8c%97%e5%a4%a7%e5%ad%a6%e8%83%a1%e5%90%91%e4%b8%9c%e8%af%be%e9%a2%98%e7%bb%84angew%ef%bc%9a-spiroxins-a%ef%bc%8cc%e4%b8%8ed%e7%9a%84%e4%b8%8d%e5%af%b9%e7%a7%b0%e5%85%a8%e5%90%88","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2021\/09\/%e8%a5%bf%e5%8c%97%e5%a4%a7%e5%ad%a6%e8%83%a1%e5%90%91%e4%b8%9c%e8%af%be%e9%a2%98%e7%bb%84angew%ef%bc%9a-spiroxins-a%ef%bc%8cc%e4%b8%8ed%e7%9a%84%e4%b8%8d%e5%af%b9%e7%a7%b0%e5%85%a8%e5%90%88.html","title":{"rendered":"\u897f\u5317\u5927\u5b66\u80e1\u5411\u4e1c\u8bfe\u9898\u7ec4Angew\uff1a (-)-Spiroxins A\uff0cC\u4e0eD\u7684\u4e0d\u5bf9\u79f0\u5168\u5408\u6210"},"content":{"rendered":"

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

\u5bfc\u8bfb<\/h4>\n

Spiroxins\u00a0A\u3001C\u4e0eD\u662f\u5728\u6d77\u6d0b\u771f\u83cc\u83cc\u682a (marine fungal strain) LL-37H248\u4e2d\u5206\u79bb\u9274\u5b9a\u51fa\u7684\u4ee3\u8c22\u4ea7\u7269\uff0c\u56e0\u5176\u5177\u6709\u72ec\u7279\u7684\u591a\u73af\u7ed3\u6784\uff0c\u800c\u5907\u53d7\u5408\u6210\u5316\u5b66\u5bb6\u7684\u5e7f\u6cdb\u5173\u6ce8\u3002\u8fd1\u65e5\uff0c\u897f\u5317\u5927\u5b66\u80e1\u5411\u4e1c\u8bfe\u9898\u7ec4\u5728Angew. Chem. Int. Ed<\/em>.\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u57fa\u4e8e5-\u53d6\u4ee3\u8418\u918c\u7684\u514b\u7ea7\u89c4\u6a21\u5bf9\u6620\u9009\u62e9\u6027\u73af\u6c27\u5316\u3001\u6c27\u5316\/\u87ba\u7f29\u916e\u5316\u4e32\u8054\u53cd\u5e94 (oxidation\/spiroketalization)\u3001\u82ef\u915a\u7ed3\u6784\u5355\u5143\u7684\u90bb\u4f4d\u9009\u62e9\u6027\u6c2f\u5316\u4ee5\u53ca\u809f\u916f\u5bfc\u5411\u7684\u4e59\u9170\u6c27\u57fa\u5316\u7684\u5173\u952e\u53cd\u5e94\u6b65\u9aa4\uff0c\u8fdb\u800c\u5b9e\u73b0(-)-Spiroxins A\u4e0eC\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5168\u5408\u6210\u4ee5\u53ca(-)-Spiroxins D\u7684\u9996\u6b21\u5168\u5408\u6210\u3002<\/p>\n

Enantioselective Total Synthesis of (-)-Spiroxins A, C and D
\nX. Shu, C. Chen, T. Yu, J. Yang, X. Hu, Angew. Chem. Int. Ed.<\/em> 2021<\/strong>, 60, 18514. doi: 10.1002\/anie.202105921<\/u><\/a>.<\/u><\/p><\/blockquote>\n

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

\u6b63\u6587<\/h4>\n

\u6d77\u6d0b\u771f\u83cc (Marine fungi)\u5df2\u7ecf\u6210\u4e3a\u5177\u6709\u5206\u5b50\u7ed3\u6784\u591a\u6837\u5316\u7684\u76f8\u5173\u4ee3\u8c22\u4ea7\u7269\u7684\u91cd\u8981\u6765\u6e90\u30021999\u5e74\uff0cMcDonald\u7b49[1]<\/sup>\u9996\u6b21\u62a5\u9053\u5728\u771f\u83cc\u83cc\u682aLL-37H248\u4e2d\uff0c\u5206\u79bb\u51fa\u76f8\u5e94\u7684\u5929\u7136\u4ea7\u7269Spiroxins A-E\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0cSpiroxin A\u5728\u5177\u6709\u4f18\u826f\u7684\u6297\u80bf\u7624\u6d3b\u6027\u4e0e\u6297\u83cc\u6d3b\u6027\u3002\u5728\u5206\u5b50\u7ed3\u6784\u4e2d\uff0cSpiroxins A-E\u5177\u6709\u5171\u540c\u7684\u4e24\u91cd\u8418\u918c\u73af\u6c27\u5316\u7269\u901a\u8fc7C-C\u952e\u4ee5\u53ca\u87ba\u73af\u7f29\u916e\u5355\u5143\u7ed3\u5408\u5f62\u6210\u7684\u591a\u73af\u9aa8\u67b6\u7ed3\u6784I<\/strong>\u00a0(Figure 1)\u3002\u540c\u65f6\uff0c\u8fd9\u4e00\u626d\u66f2\u7684\u7c7b\u7b3c\u72b6\u9aa8\u67b6 (distorted cage-like frame)\u4e2d\u5177\u6709\u516d\u6216\u4e03\u91cd\u7684\u7acb\u4f53\u4e2d\u5fc3\u3002<\/p>\n

2003\u5e74\uff0cImanishi\u7b49[2]<\/sup>\u9996\u6b21\u91c7\u7528TBAF\u6d3b\u7684\u5316Suzuki-Miyaura\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\u4f5c\u4e3a\u5173\u952e\u6b65\u9aa4\uff0c\u9996\u6b21\u5b9e\u73b0(\u00b1)-Spiroxin C\u7684\u5168\u5408\u6210\u30022017\u5e74\uff0c\u57fa\u4e8e\u8418\u918c\u884d\u751f\u7269\u7acb\u4f53\u4e13\u4e00\u6027\u5206\u5b50\u5185\u5149\u6c27\u5316\u8fd8\u539f\u53cd\u5e94\u7b56\u7565\uff0cSuzuki\u7b49[3]<\/sup>\u9996\u6b21\u5b8c\u6210(-)-Spiroxin C\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5168\u5408\u6210\u3002\u4e4b\u540e\uff0cSuzuki\u7b49[4]<\/sup>\u62a5\u9053\u91c7\u7528\u5149\u8f90\u5c04\u6216\u9178\/\u78b1\u6761\u4ef6\u5f15\u53d1\u7684\u4e24\u79cd\u4e0d\u540c\u7684\u4e32\u8054\u53cd\u5e94\u65b9\u6cd5\u5b66\u7b56\u7565\uff0c\u5206\u522b\u4f7f\u76f8\u540c\u4e2d\u95f4\u4f53\u7684\u7edd\u5bf9\u6784\u578b\u53d1\u751f\u4fdd\u6301\u4e0e\u7ffb\u8f6c\u3002\u540c\u65f6\uff0cSuzuki\u56e2\u961f\u901a\u8fc7\u4e0a\u8ff0\u7b56\u7565\u4f5c\u4e3a\u5173\u952e\u6b65\u9aa4\uff0c\u9996\u6b21\u5b8c\u6210Spiroxin A\u7684\u4e24\u79cd\u5bf9\u6620\u4f53\u7684\u5168\u5408\u6210\u3002<\/p>\n

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

Spiroxin\u00a0D\u4e0eSpiroxin\u00a0C\u5206\u5b50\u4e2d\u5b58\u5728\u7684\u552f\u4e00\u5dee\u522b\u5728\u4e8eC1\u4f4d\u7684\u7f9f\u57fa (\u5176\u76f8\u5bf9\u6784\u578b\u672a\u77e5)\uff0c\u800cSpiroxin A\u4e0eSpiroxin\u00a0C\u7684\u5dee\u522b\u5219\u5728\u4e8e\uff0cSpiroxin A\u5206\u5b50\u4e2d\u5177\u6709\u591a\u91cd\u7684\u7f9f\u57fa\u5b98\u80fd\u56e2\uff0c\u5e76\u5b58\u5728\u6c2f\u53d6\u4ee3\u57fa\u3002\u7531\u6b64\uff0c\u4f5c\u8005\u8bbe\u60f3\uff0cSpiroxin\u00a0C\u53ef\u80fd\u4f5c\u4e3a\u5408\u6210Spiroxin\u00a0A\u4e0eD\u7684\u5171\u540c\u4e2d\u95f4\u4f53\u3002\u540c\u65f6\uff0c\u5bf9\u4e8e\u6838\u5fc3\u591a\u73af\u9aa8\u67b6\u7684\u6784\u5efa\uff0c\u4f5c\u8005\u8bbe\u60f3\u901a\u8fc75<\/strong>\u7684\u6c27\u5316\u4ee5\u53ca\u540e\u7eed\u87ba\u7f29\u916e\u5316\u7684\u4e00\u6b65\u4e32\u8054\u53cd\u5e94\u8fc7\u7a0b\u800c\u5b9e\u73b0\u3002\u5176\u4e2d\uff0c\u901a\u8fc7\u9009\u62e9\u9502\u8bd5\u52424<\/strong>\u4e0e\u624b\u6027\u03b1<\/em>,\u03b2<\/em>-\u73af\u6c27\u916e3<\/strong>\u4e4b\u95f4\u7684\u975e\u5bf9\u6620\u9009\u62e9\u6027\u52a0\u6210\u7b56\u7565\uff0c\u5b8c\u62105<\/strong>\u7684\u5236\u5907\u3002\u800c3<\/strong>\u4e0e4<\/strong>\u5747\u53ef\u7531\u5546\u54c1\u5316\u7684juglone\u00a01<\/strong>\u8fdb\u884c\u5236\u5907\uff0c\u5e76\u80fd\u591f\u91c7\u7528\u5bf9\u6620\u9009\u62e9\u6027\u73af\u6c27\u5316\u8fc7\u7a0b\uff0c\u57282<\/strong>\u5206\u5b50\u4e2d\u5f15\u5165\u521d\u59cb\u7684\u624b\u6027\u7acb\u4f53\u751f\u6210\u4e2d\u5fc3\uff0c\u8fdb\u800c\u80fd\u591f\u6210\u529f\u5b9e\u73b0Spiroxins\u00a0A\u3001C\u4ee5\u53caD\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5168\u5408\u6210\u3002<\/p>\n

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

\u8be5\u5c0f\u7ec4\u9762\u4e34\u7684\u9996\u8981\u6311\u6218\u5728\u4e8e\u5b9e\u73b0\u624b\u6027\u03b1<\/em>,\u03b2<\/em>-\u73af\u6c27\u916e3<\/strong>\u7684\u9ad8\u5ea6\u5bf9\u6620\u9009\u62e9\u6027\u5408\u6210\u3002\u4f5c\u8005\u9996\u5148\u901a\u8fc7\u5e02\u552e\u7684juglone\u00a01<\/strong>\uff0c\u5b8c\u6210\u5316\u5408\u72696<\/strong>\u7684\u5236\u5907\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u5bf95-\u53d6\u4ee3\u8418\u918c6<\/strong>\u7684\u5bf9\u6620\u9009\u62e9\u6027\u73af\u6c27\u5316\u53cd\u5e94\u4e2d\u7684\u4e0d\u5bf9\u79f0\u76f8\u8f6c\u79fb\u50ac\u5316\u5242\u8fdb\u884c\u7b5b\u9009 (Table 1,\u00a0C-1<\/strong>\u81f3C-13<\/strong>)\u3002\u7814\u7a76\u8868\u660e\uff0c\u91c7\u7528C-11<\/strong>\u65f6\uff0c\u5728\u76f8\u5e94\u7684\u514b\u7ea7\u89c4\u6a21\u5b9e\u9a8c\u4e2d\uff0c\u80fd\u591f\u83b7\u5f9796%\u6536\u7387\u7684\u73af\u6c27\u5316\u4ea7\u72692<\/strong>\uff0cee\u4e3a80%\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u89c2\u5bdf\u5230\uff0c\u901a\u8fc7\u91cd\u7ed3\u6676\u8fc7\u7a0b\uff0c\u80fd\u591f\u5b9e\u73b0\u6709\u6548\u7684\u5bf9\u6620\u4f53\u5bcc\u96c6 (>99% ee)\u3002<\/p>\n

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

\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u5f00\u59cb\u8fdb\u884c(-)-Spiroxin C\u7684\u5168\u5408\u6210\u65b9\u6848\u8bbe\u8ba1 (Scheme 2)\u3002\u9996\u5148\uff0c\u4f5c\u8005\u5bf9\u624b\u6027\u73af\u6c27\u5316\u72692<\/strong>\u76f8\u5173\u7684\u8fd8\u539f\u53cd\u5e94\u6761\u4ef6\u8fdb\u884c\u6df1\u5165\u7814\u7a76\u3002\u8fdb\u800c\u89c2\u5bdf\u5230\uff0c\u5728\u91c7\u7528(CH3<\/sub>)4<\/sub>NBH(OAc)3<\/sub>\u4f5c\u4e3a\u8fd8\u539f\u5242\u65f6\uff0c\u80fd\u591f\u83b7\u5f97\u4f18\u826f\u7684\u533a\u57df\u4e0e\u975e\u5bf9\u6620\u9009\u62e9\u6027\uff0c\u5e76\u901a\u8fc7\u540e\u7eed\u7684\u7f9f\u57fa\u4fdd\u62a4\u6b65\u9aa4\uff0c\u5f62\u6210\u4ea7\u72693<\/strong>\u3002X<\/em>-\u5c04\u7ebf\u6676\u4f53\u5b66\u7814\u7a76\u8868\u660e\uff0c\u4ea7\u72693<\/strong>\u4e2d\u73af\u6c27\u5316\u7269\u7247\u6bb5\u7684\u7edd\u5bf9\u6784\u578b\u4e0e(-)-Spiroxins A\u4ee5\u53caC\u4e2d\u7684\u73af\u6c27\u5316\u7269\u7247\u6bb5\u76f8\u540c\u3002\u540c\u65f6\uff0cjuglone\u00a01<\/strong>\u7ecf\u82c4\u57fa\u4fdd\u62a4\u3001\u918c\u8fd8\u539f-\u4e8c\u7532\u57fa\u5316\u4ee5\u53ca\u6eb4\u5316\u7684\u4e09\u6b65\u53cd\u5e94\u8fc7\u7a0b\uff0c\u5f62\u6210\u82b3\u57fa\u6eb4\u4ea7\u72697<\/strong>\u3002\u4e4b\u540e\uff0c\u73af\u6c27\u5316\u72693<\/strong>\u4e0e\u901a\u8fc7\u82b3\u57fa\u6eb47<\/strong>\u539f\u4f4d\u5f62\u6210\u7684\u82b3\u57fa\u9502\u8bd5\u5242\u4f5c\u7528\uff0c\u5e76\u7ecf\u5386\u8fdb\u4e00\u6b65\u7684\u82c4\u57fa\u4e0e4-\u7532\u57fa\u82c4\u57fa\u53bb\u9664\u6b65\u9aa4\u4e4b\u540e\uff0c\u5f62\u6210\u780c\u57575<\/strong>\u3002\u63a5\u4e0b\u6765\uff0c\u8be5\u5c0f\u7ec4\u8bbe\u60f3\uff0c\u901a\u8fc7\u87ba\u7f29\u916e\u5355\u5143\u7684\u5f15\u5165\uff0c\u8fdb\u800c\u987a\u5229\u5b8c\u6210\u5206\u5b50\u4e2d\u6838\u5fc3\u591a\u73af\u9aa8\u67b6\u7684\u6784\u5efa\u3002\u8fd9\u91cc\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5728\u91c7\u7528\u6c27\u5316\u94f6(II)\u4e0e\u78f7\u9178\u6c27\u5316\u4f53\u7cfb[5]<\/sup>\u65f6\uff0c\u80fd\u591f\u6210\u529f\u83b7\u5f9760%\u6536\u7387\u7684\u87ba\u7f29\u916e\u4ea7\u72698<\/strong>\u3002\u5176\u4e2d\uff0c\u78f7\u9178\u7684\u5b58\u5728\u5bf9\u4e8e\u6c27\u5316\/\u87ba\u7f29\u916e\u5316\u4e32\u8054\u53cd\u5e94\u8fc7\u7a0b\u7684\u987a\u5229\u8fdb\u884c\u5c24\u4e3a\u5173\u952e (\u53c2\u9605Supporting Information<\/u><\/a>)\u3002\u4e4b\u540e\uff0c\u901a\u8fc7\u540e\u7eed\u7684\u53bb\u9664TBS\u4fdd\u62a4\u57fa\u56e2\u3001\u7f9f\u57fa\u5b98\u80fd\u56e2\u7684\u6c27\u5316\u4ee5\u53ca\u73af\u6c27\u5316\u6b65\u9aa4\uff0c\u8fdb\u800c\u987a\u5229\u5b8c\u6210(-)-Spiroxin C\u5206\u5b50\u7684\u5168\u5408\u6210\u3002\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u8fdb\u884cC1\u6784\u578b\u672a\u77e5\u7684\u00a0(\u2013)-spiroxin D\u7684\u5168\u5408\u6210\u7814\u7a76\u3002\u5b9e\u9a8c\u53d1\u73b0\uff0c\u5728\u91c7\u7528DIBAL-H\u8fd8\u539f(\u2013)-Spiroxin\u00a0C\u4e2d\u7684C1\u7fb0\u57fa\u65f6\uff0c\u80fd\u591f\u76f4\u63a5\u83b7\u5f97(\u2013)-Spiroxin\u00a0D\uff0c\u5e76\u8868\u73b0\u51fa\u4f18\u826f\u7684\u533a\u57df\u9009\u62e9\u6027\u4e0e\u975e\u5bf9\u6620\u9009\u62e9\u6027\u3002\u540c\u65f6\uff0c\u901a\u8fc7\u4e0a\u8ff0\u8f6c\u5316\u8fc7\u7a0b\uff0c\u5e76\u8fdb\u4e00\u6b65\u7ed3\u5408X<\/em>-\u5c04\u7ebf\u6676\u4f53\u5b66\u5206\u6790\uff0c\u8fdb\u800c\u987a\u5229\u786e\u5b9a\u00a0(\u2013)-spiroxin D\u5206\u5b50\u4e2dC1\u4f4d\u7f6e\u7684\u7edd\u5bf9\u6784\u578b\u3002<\/p>\n

\u6700\u540e\uff0c\u4e3a\u5b8c\u6210(-)-Spiroxin\u00a0A\u7684\u5168\u5408\u6210\uff0c\u4f5c\u8005\u9996\u5148\u5bf9 (-)-SpiroxinC\u5206\u5b50\u4e2d\u82ef\u915a\u7247\u6bb5\u7684\u90bb\u4f4d\u9009\u62e9\u6027\u6c2f\u5316\u8fc7\u7a0b\u8fdb\u884c\u6df1\u5165\u7814\u7a76\u3002\u5b9e\u9a8c\u8868\u660e\uff0c\u5728\u91c7\u75281,3-\u4e8c\u6c2f-5,5-\u4e8c\u7532\u57fa\u4e59\u5185\u9170\u8132 (1,3-dichloro-5,5-dimethylhydantoin, DCDMH)\u4f5c\u4e3a\u6c2f\u5316\u8bd5\u5242\u65f6\uff0c\u80fd\u591f\u83b7\u5f9773%\u6536\u7387\u7684\u6c2f\u5316\u4ea7\u72699<\/strong>\u3002\u540c\u65f6\uff0c(-)-Spiroxin\u00a0A\u7684\u5168\u5408\u6210\u8bbe\u8ba1\u4e2d\u9762\u4e34\u7684\u5de8\u5927\u6311\u6218\uff0c\u5219\u5728\u4e8e\u533a\u57df\u9009\u62e9\u6027\u5730\u5c06\u7f9f\u57fa\u5f15\u5165\u81f3(-)-Spiroxin\u00a0A\u5206\u5b50\u4e2d\u6700\u4e0b\u7aef\u7684\u82b3\u73af\u7247\u6bb5\u3002\u5176\u4e2d\uff0c\u4f5c\u8005\u8bbe\u60f3\uff0c\u91c7\u7528\u809f\u916f\u5bfc\u5411\u7684\u4e59\u9170\u6c27\u57fa\u5316\u53cd\u5e94\u7b56\u7565[6]<\/sup>\u5c06\u80fd\u591f\u6709\u6548\u5730\u89e3\u51b3\u4e0a\u8ff0\u95ee\u9898\u3002\u5e76\u4e14\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u9009\u62e9K2<\/sub>S2<\/sub>O8<\/sub>\u4f5c\u4e3a\u6c27\u5316\u5242\u65f6\uff0c\u80fd\u591f\u83b7\u5f9762%\u6536\u7387\u7684\u5173\u952e\u780c\u575711<\/strong>\u3002\u63a5\u4e0b\u6765\uff0c\u901a\u8fc7\u53bb\u9664\u5206\u5b50\u4e2d\u5168\u90e8\u7684\u4e59\u9170\u57fa\u4fdd\u62a4\u57fa\u4e0e\u809f\u916f\u57fa\u56e2\u4e4b\u540e\uff0c\u6700\u7ec8\u5b8c\u6210(-)-Spiroxin A\u7684\u5168\u5408\u6210\u3002<\/p>\n

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\u603b\u7ed3<\/h4>\n

\u897f\u5317\u5927\u5b66\u80e1\u5411\u4e1c\u8bfe\u9898\u7ec4\u5206\u522b\u901a\u8fc710\u300111\u4ee5\u53ca14\u6b65\u7684\u53cd\u5e94\u8bbe\u8ba1\u65b9\u6848\uff0c\u987a\u5229\u5b8c\u6210(-)-Spiroxins C\u3001D\u4e0eA\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5168\u5408\u6210\u3002\u5176\u4e2d\uff0c\u5173\u952e\u7684\u53cd\u5e94\u6b65\u9aa4\u6d89\u53ca5-\u53d6\u4ee3\u8418\u918c\u7684\u5bf9\u6620\u9009\u62e9\u6027\u73af\u6c27\u5316\u3001\u6c27\u5316\/\u87ba\u7f29\u916e\u5316\u4e32\u8054\u53cd\u5e94\u3001\u901a\u8fc7DCDMH\u53c2\u4e0e\u7684\u82ef\u915a\u7247\u6bb5\u7684\u90bb\u4f4d\u9009\u62e9\u6027\u6c2f\u5316\u4ee5\u53ca\u809f\u916f\u5bfc\u5411\u7684\u4e59\u9170\u6c27\u57fa\u5316\u8fc7\u7a0b\u3002<\/p>\n

\u53c2\u8003\u6587\u732e<\/h4>\n[1] L. A. McDonald, D. R. Abbanat, L. R. Barbieri, V. S. Bernan, C. M.\u00a0Discafani, M. Greenstein, K. Janota, J. D. Korshalla, P. Lassota, M.Tischler, G. T. Carter, Tetrahedron Lett<\/i><\/em>. 1999<\/b><\/strong>, 40<\/em>, 2489. doi: 10.1016\/S0040-4039(99)00242-7<\/u><\/a>.<\/p>\n[2] K. Miyashita, T. Sakai, T. Imanishi, Org. Lett. <\/i><\/em>2003<\/b><\/strong>, 5<\/em>, 2683.\u00a0doi: 10.1021\/ol034856v<\/u><\/a>.<\/u><\/p>\n[3] a) Y. Ando, A. Hanaki, R. Sasaki, K. Ohmori, K. Suzuki, Angew. Chem.<\/i><\/em>\u00a0<\/i><\/em>Int. Ed. <\/i><\/em>2017<\/b><\/strong>, 56<\/em>, 11460. doi :10.1021\/ol034856v<\/u><\/a>.b) F. Wakita, Y. Ando, K. Ohmori, K. Suzuki, Lett. <\/i><\/em>2018<\/b><\/strong>, 20<\/em>, 3928. doi : 10.1021\/acs.orglett.8b01475<\/u><\/a>.<\/p>\n[4] Y. Ando, D. Tanaka, R. Sasaki, K. Ohmori, K. Suzuki, Angew. Chem. Int. Ed. <\/i><\/em>2019<\/b><\/strong>, 36<\/em>, 12637. doi: 10.1002\/ange.201906762<\/u><\/a>.<\/p>\n[5]\u00a0L. Syper, Tetrahedron Lett<\/i><\/em>. 1967<\/b><\/strong>, 8<\/em>,\u00a04193.\u00a0doi: 10.1016\/S0040-4039(01)89720-3<\/u><\/a>.<\/u>b) C. D. Snyder, H. Rapoport, Am. Chem. Soc<\/i><\/em>.1972<\/b><\/strong>, 94<\/em>, 227.doi: 10.1021\/ja00756a040<\/u><\/a>.<\/u><\/p>\n[6]\u00a0a) L. V. Desai, K. L. Hull, M. S. Sanford, J. Am. Chem. Soc<\/i><\/em>. 2004<\/b><\/strong>, 126<\/em>,\u00a09542.\u00a0doi: 10.1021\/ja046831c<\/u><\/a>.<\/u>b) L. V. Desai, H. A. Malik, M. S. Sanford, Org<\/i><\/em>. Lett<\/i><\/em>. 2006<\/b><\/strong>,8<\/em>, 1141.doi: 1021\/ol0530272<\/u><\/a>. <\/u>c) R. Saha, N. Perveen, N.Nihesh, G. Sekara, Adv<\/i><\/em>. Synth<\/i><\/em>. Catal<\/i><\/em>. 2019<\/b><\/strong>, 361<\/em>, 510.doi: 1002\/adsc.201801340<\/u><\/a>. <\/u>d) M.Schneider, M. J. R. Richter, S. Krautwald, E. M. Carreira, Org<\/i><\/em>. Lett<\/i><\/em>. 2019<\/b><\/strong>,21<\/em>, 8705.\u00a0doi: 1021\/acs.orglett.9b03303<\/u><\/a>. <\/u>e) M. Haider, G. Sennari, A. Eggert, R. Sarpong, Am.Chem. Soc. <\/i><\/em>2021<\/b><\/strong>, 143<\/em>, 2710.doi: 10.1021\/jacs.1c00293<\/u><\/a>.<\/u><\/p>\n","protected":false},"excerpt":{"rendered":"\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749 \u5bfc\u8bfb Spiroxins\u00a0A\u3001C\u4e0eD\u662f\u5728\u6d77\u6d0b\u771f\u83cc\u83cc\u682a (marine fungal strain) LL-37H248\u4e2d\u5206\u79bb\u9274\u5b9a\u51fa\u7684\u4ee3\u8c22\u4ea7\u7269\uff0c\u56e0\u5176\u5177\u6709\u72ec\u7279\u7684\u591a\u73af\u7ed3\u6784\uff0c\u800c\u5907\u53d7\u5408\u6210\u5316\u5b66\u5bb6\u7684\u5e7f\u6cdb\u5173\u6ce8\u3002\u8fd1\u65e5\uff0c\u897f\u5317\u5927\u5b66\u80e1\u5411\u4e1c\u8bfe\u9898\u7ec4\u5728Angew. Chem. Int. Ed.\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u57fa\u4e8e5-\u53d6\u4ee3\u8418\u918c\u7684\u514b\u7ea7\u89c4\u6a21\u5bf9\u6620\u9009\u62e9\u6027\u73af\u6c27\u5316\u3001\u6c27\u5316\/\u87ba\u7f29\u916e\u5316\u4e32\u8054\u53cd\u5e94 (oxidation\/spiroketalization)\u3001\u82ef\u915a\u7ed3\u6784\u5355\u5143\u7684\u90bb\u4f4d\u9009\u62e9\u6027\u6c2f\u5316\u4ee5\u53ca\u809f\u916f\u5bfc\u5411\u7684\u4e59\u9170\u6c27\u57fa\u5316\u7684\u5173\u952e\u53cd\u5e94\u6b65\u9aa4\uff0c\u8fdb\u800c\u5b9e\u73b0(-)-Spiroxins A\u4e0eC\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5168\u5408\u6210\u4ee5\u53ca(-)-Spiroxins D\u7684\u9996\u6b21\u5168\u5408\u6210\u3002 Enantioselective Total Synthesis of (-)-Spiroxins A, C and D X. Shu, C. Chen, T. Yu, J. Yang, X. Hu, Angew. Chem. Int. Ed. 2021, 60, 18514. doi: 10.1002\/anie.202105921. \u6b63\u6587 \u6d77\u6d0b\u771f\u83cc (Marine fungi)\u5df2\u7ecf\u6210\u4e3a\u5177\u6709\u5206\u5b50\u7ed3\u6784\u591a\u6837\u5316\u7684\u76f8\u5173\u4ee3\u8c22\u4ea7\u7269\u7684\u91cd\u8981\u6765\u6e90\u30021999\u5e74\uff0cMcDonald\u7b49[1]\u9996\u6b21\u62a5\u9053\u5728\u771f\u83cc\u83cc\u682aLL-37H248\u4e2d\uff0c\u5206\u79bb\u51fa\u76f8\u5e94\u7684\u5929\u7136\u4ea7\u7269Spiroxins A-E\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0cSpiroxin A\u5728\u5177\u6709\u4f18\u826f\u7684\u6297\u80bf\u7624\u6d3b\u6027\u4e0e\u6297\u83cc\u6d3b\u6027\u3002\u5728\u5206\u5b50\u7ed3\u6784\u4e2d\uff0cSpiroxins A-E\u5177\u6709\u5171\u540c\u7684\u4e24\u91cd\u8418\u918c\u73af\u6c27\u5316\u7269\u901a\u8fc7C-C\u952e\u4ee5\u53ca\u87ba\u73af\u7f29\u916e\u5355\u5143\u7ed3\u5408\u5f62\u6210\u7684\u591a\u73af\u9aa8\u67b6\u7ed3\u6784I\u00a0(Figure 1)\u3002\u540c\u65f6\uff0c\u8fd9\u4e00\u626d\u66f2\u7684\u7c7b\u7b3c\u72b6\u9aa8\u67b6 (distorted cage-like frame)\u4e2d\u5177\u6709\u516d\u6216\u4e03\u91cd\u7684\u7acb\u4f53\u4e2d\u5fc3\u3002 2003\u5e74\uff0cImanishi\u7b49[2]\u9996\u6b21\u91c7\u7528TBAF\u6d3b\u7684\u5316Suzuki-Miyaura\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\u4f5c\u4e3a\u5173\u952e\u6b65\u9aa4\uff0c\u9996\u6b21\u5b9e\u73b0(\u00b1)-Spiroxin C\u7684\u5168\u5408\u6210\u30022017\u5e74\uff0c\u57fa\u4e8e\u8418\u918c\u884d\u751f\u7269\u7acb\u4f53\u4e13\u4e00\u6027\u5206\u5b50\u5185\u5149\u6c27\u5316\u8fd8\u539f\u53cd\u5e94\u7b56\u7565\uff0cSuzuki\u7b49[3]\u9996\u6b21\u5b8c\u6210(-)-Spiroxin C\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5168\u5408\u6210\u3002\u4e4b\u540e\uff0cSuzuki\u7b49[4]\u62a5\u9053\u91c7\u7528\u5149\u8f90\u5c04\u6216\u9178\/\u78b1\u6761\u4ef6\u5f15\u53d1\u7684\u4e24\u79cd\u4e0d\u540c\u7684\u4e32\u8054\u53cd\u5e94\u65b9\u6cd5\u5b66\u7b56\u7565\uff0c\u5206\u522b\u4f7f\u76f8\u540c\u4e2d\u95f4\u4f53\u7684\u7edd\u5bf9\u6784\u578b\u53d1\u751f\u4fdd\u6301\u4e0e\u7ffb\u8f6c\u3002\u540c\u65f6\uff0cSuzuki\u56e2\u961f\u901a\u8fc7\u4e0a\u8ff0\u7b56\u7565\u4f5c\u4e3a\u5173\u952e\u6b65\u9aa4\uff0c\u9996\u6b21\u5b8c\u6210Spiroxin A\u7684\u4e24\u79cd\u5bf9\u6620\u4f53\u7684\u5168\u5408\u6210\u3002 Spiroxin\u00a0D\u4e0eSpiroxin\u00a0C\u5206\u5b50\u4e2d\u5b58\u5728\u7684\u552f\u4e00\u5dee\u522b\u5728\u4e8eC1\u4f4d\u7684\u7f9f\u57fa (\u5176\u76f8\u5bf9\u6784\u578b\u672a\u77e5)\uff0c\u800cSpiroxin A\u4e0eSpiroxin\u00a0C\u7684\u5dee\u522b\u5219\u5728\u4e8e\uff0cSpiroxin 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A. McDonald, D. R. Abbanat, L. R. Barbieri, V. S. Bernan, C. M.\u00a0Discafani, M. Greenstein, K. Janota, J. D. Korshalla, P. 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