{"id":15444,"date":"2017-09-08T06:04:32","date_gmt":"2017-09-07T22:04:32","guid":{"rendered":"\/\/www.gsbet888.com\/?p=15444"},"modified":"2019-08-02T18:52:48","modified_gmt":"2019-08-02T10:52:48","slug":"iwao-%e5%90%b2%e5%93%9a%e5%90%88%e6%88%90","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/reactions\/2017\/09\/iwao-%e5%90%b2%e5%93%9a%e5%90%88%e6%88%90.html","title":{"rendered":"Iwao \u5432\u54da\u5408\u6210"},"content":{"rendered":"
Iwao \u5432\u54da\u5408\u6210(Iwao indole synthesis)\u6d89\u53caN<\/em>-\u53d4\u4e01\u6c27\u7fb0\u57fa\u82ef\u80fa\u7684\u5728\u53d4\u4e01\u57fa\u9502\u4f5c\u7528\u4e0b\u7684DoM\u53cd\u5e94(Directed ortho metalation)\u3001\u91c7\u75281-\u4e09\u70f7\u57fa\u7845\u57fa-1-\u82ef\u4e9a\u78fa\u9170\u57fa\u4e59\u70ef\u5bf9\u7684\u6709\u673a\u9502\u4e2d\u95f4\u4f53\u7684\u6dec\u706d\u3001\u70edsila-Pummerer \u91cd\u6392\u83b7\u5f972-thioindolines\u3001\u91c7\u7528m-CPBA\u5bf92-2-thioindolines\u7684\u6c27\u5316\u751f\u53ca\u4e9a\u781c\u7684syn<\/em>-\u6d88\u9664\u7b49\u4e94\u4e2a\u53cd\u5e94\u8fc7\u7a0b\uff0c\u6700\u7ec8\u83b7\u5f97\u76f8\u5e94\u5432\u54da\u5316\u5408\u7269\u3002\u65e0Boc\u4fdd\u62a4\u57fa\u7684\u82ef\u80fa\u5316\u5408\u7269\u53caN<\/em>-\u7279\u620a\u9170\u57fa\u82ef\u80fa(\u5728N<\/em>-\u53d4\u4e01\u6c27\u7fb0\u57fa-3-\u82ef\u80fa\u7684DoM\u53cd\u5e94\u96be\u4ee5\u8fdb\u884c\u65f6\uff0c\u53ef\u91c7\u7528N-\u7279\u620a\u9170\u57fa\u82ef\u80fa\u53ef\u4f5c\u4e3a\u5176\u66ff\u4ee3\u7269)\u540c\u6837\u53ef\u4ee5\u53c2\u4e0e\u8be5\u53cd\u5e94\u8fc7\u7a0b\u3002\u8be5\u53cd\u5e94\u7531\u65e5\u672c\u957f\u5d0e\u5927\u5b66(Nagasaki University)\u7684\u5ca9\u5c3e\u6b63\u4f26(Iwao Masatomo)\u7814\u7a76\u7ec4\u57281994\u5e74\u9996\u6b21\u62a5\u9053\u3002\u76ee\u524d\uff0c\u8be5\u53cd\u5e94\u4e3b\u8981\u7528\u4e8e\u5432\u54da\u7c7b\u6742\u73af\u5316\u5408\u7269\u7684\u5408\u6210\u3002<\/p>\n \u5432\u54da\u53ca\u5432\u54da\u6797\u7c7b\u5316\u5408\u7269\u7684\u5408\u6210[1]\n \u5b9e\u9a8c\u6b65\u9aa4<\/strong><\/p>\n \u5432\u54da\u5549\u7c7b\u5316\u5408\u7269\u7684\u5408\u6210<\/strong>[1] [2]\uff1a<\/strong>\u5728-78o<\/sup>C\uff0c\u6c2e\u6c14\u6c14\u6c1b\u4e0b\uff0c\u5c062M \u7684\u53d4\u4e01\u57fa\u9502 (2.4 eq.)\u7684\u620a\u70f7\u6eb6\u6db2\u6ef4\u52a0\u81f3N-\u53d4\u4e01\u6c27\u7fb0\u57fa\u82ef\u80fa (l eq.) \u7684\u65e0\u6c34THF\u6eb6\u6db2(0.4 M)\u4e2d\u3002\u6405\u62cc15 min\u540e\uff0c\u5c06\u4e0a\u8ff0\u6eb6\u6db2\u5347\u6e29\u81f3-20o<\/sup>C\uff0c\u7ee7\u7eed\u6405\u62cc3 h\u3002\u518d\u5411\u4e0a\u8ff0\u6eb6\u6db2\u4e2d\u52a0\u51651-\u4e09\u70f7\u57fa\u7845\u57fa-1-\u82ef\u4e9a\u78fa\u9170\u57fa\u4e59\u70ef(1.5 eq.)\uff0c\u5e76\u7ee7\u7eed\u5728-20o<\/sup>C\u4e0b\u6405\u62cc2 h\u3002\u53cd\u5e94\u7ed3\u675f\u540e\uff0c\u91c7\u7528sat. NH4<\/sub>Cl\u6eb6\u6db2\u6dec\u706d\u53cd\u5e94\uff0c\u540e\u5c06\u53cd\u5e94\u6db2\u7528\u4e59\u9178\u4e59\u916f\u8fdb\u884c\u8403\u53d6\uff0c\u518d\u5c06\u8403\u53d6\u6db2\u56de\u6d411 h\u3002\u51cf\u538b\u9664\u53bb\u6eb6\u5242\u540e\uff0c\u5c06\u7c97\u4ea7\u7269\u91c7\u7528\u7845\u80f6\u67f1\u8272\u8c31(\u6b63\u5df1\u70f7\/\u4e59\u9178\u4e59\u916f 20:1 v\/v \u4f5c\u4e3a\u6d17\u8131\u5242)\u5206\u79bb\u7eaf\u5316\uff0c\u83b7\u5f97\u76f8\u5e94\u5432\u54da\u5549\u7c7b\u5316\u5408\u7269\u3002<\/p>\n \u5432\u54da\u5549\u7c7b\u5316\u5408\u7269\u7684\u6c27\u5316<\/strong>[3]\uff1a<\/strong>\u5c06\u5432\u54da\u5549(l eq.)\u7684\u4e8c\u6c2f\u7532\u70f7\u6eb6\u6db2(0.05 M)\u51b7\u5374\u81f3-78o<\/sup>C\uff0c\u540e\u7528\u6ce8\u5c04\u5668\u5c06\u95f4\u6c2f\u8fc7\u82ef\u7532\u9178(l eq.)\u7684\u4e8c\u6c2f\u7532\u70f7\u6eb6\u6db2(0.15 M)\u6ef4\u52a0\u81f3\u4e0a\u8ff0\u5747\u76f8\u6eb6\u6db2\u4e2d(\u8d85\u8fc75 min\u540e\uff0c\u6ef4\u52a0\u5b8c\u6bd5)\u3002\u6ef4\u52a0\u5b8c\u6bd5\u540e\uff0c\u5f00\u542f\u6405\u62cc\uff0c\u5e76\u7528TLC\u76d1\u63a7\uff0c\u76f4\u81f3\u53cd\u5e94\u5b8c\u6210\u3002\u53cd\u5e94\u7ed3\u675f\u540e\uff0c\u5c06\u51b7\u7684\u53cd\u5e94\u6db2\u5012\u5165\u88c5\u6709\u4e59\u919a\u53ca10%\u4e9a\u786b\u9178\u94a0\u6eb6\u6db2\u7684\u5206\u6db2\u6f0f\u6597\u4e2d\uff0c\u8403\u53d6\u5206\u51fa\u6709\u673a\u76f8\u3002\u518d\u5c06\u6709\u673a\u76f8\u7528\u9971\u548c\u78b3\u9178\u6c22\u94a0\u6eb6\u6db2\u6d17\u6da4\u3001\u5e72\u71e5\uff0c\u51cf\u538b\u84b8\u998f\u9664\u53bb\u6eb6\u5242\u540e\uff0c\u5c06\u6240\u5f97\u7c97\u4ea7\u7269\u76f4\u63a5\u8fdb\u884c\u540e\u7eed\u7684\u6d88\u9664\u53cd\u5e94\u3002<\/p>\n \u5432\u54da\u5549\u7c7b\u5316\u5408\u7269\u7684\u6d88\u9664<\/strong>[3]\uff1a<\/strong><\/p>\n \u5c06\u6c27\u5316\u53cd\u5e94\u6240\u5f97\u7c97\u4ea7\u7269(l eq.)\u6eb6\u4e8e\u7532\u82ef(0.13 M)\u4e2d\uff0c\u5c06\u4e0a\u8ff0\u53cd\u5e94\u6df7\u5408\u7269\u52a0\u70ed\u81f3\u56de\u6d41\uff0c\u5e76\u7528TLC\u76d1\u63a7\uff0c\u76f4\u81f3\u53cd\u5e94\u5b8c\u6210\u3002\u53cd\u5e94\u7ed3\u675f\u540e\uff0c\u51cf\u538b\u84b8\u998f\u9664\u53bb\u6eb6\u5242\u3002\u5c06\u6240\u5f97\u7c97\u4ea7\u7269\u91c7\u7528\u7845\u80f6\u67f1\u8272\u8c31(\u4e09\u6c2f\u7532\u70f7\u4f5c\u4e3a\u6d17\u8131\u5242)\u5206\u79bb\u7eaf\u5316\uff0c\u83b7\u5f97\u6700\u7ec8\u76ee\u6807\u4ea7\u7269\u3002<\/p>\n \u5c0f\u7f16\u90d1\u91cd\u63d0\u793a\uff1a\u53d4\u4e01\u57fa\u9502\u63a5\u89e6\u7a7a\u6c14\u65f6\uff0c\u6781\u6613\u53d1\u751f\u81ea\u71c3\uff0c\u5b9e\u9a8c\u64cd\u4f5c\u65f6\u9700\u8981\u683c\u5916\u5c0f\u5fc3\uff0c\u4e25\u683c\u907f\u514d\u4e0e\u7a7a\u6c14\u63a5\u89e6\uff0c\u6700\u597d\u5728\u6c29\u6c14\u624b\u5957\u7bb1\u5185\u8fdb\u884c\u64cd\u4f5c\u3002<\/p>\n <\/p>\n<\/a><\/p>\n
\u57fa\u672c\u6587\u732e<\/strong><\/h4>\n[1] M. Iwao, Heterocycles, 1994, 38, 45. doi: 10.3987\/COM-93-6563.<\/a><\/p>\n
\n<\/strong><\/p>\n\u53cd\u5e94\u673a\u7406<\/strong><\/h4>\n
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\n<\/strong><\/p>\n\u53cd\u5e94\u5b9e\u4f8b<\/strong><\/h4>\n
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\u53c2\u8003\u6587\u732e<\/strong><\/h4>\n[1] M. Iwao, Heterocycles, 1994, 38, 45. doi: 10.3987\/COM-93-6563.<\/a><\/p>\n[2] J. M. Muchowski, M. C. Venuti, J. Org. Chem. 1980,45, 4801. doi: 10.1021\/jo01311a059.<\/a><\/p>\n[3] B. M. Trost, T. N. Salzmann, K. Hiroi, J. Ame. Chem. Soc., 1976, 98, 4887. doi: 10.1021\/ja00432a034.<\/a><\/p>\n
\u5b9e\u9a8c\u5b89\u5168\u987b\u77e5<\/strong><\/h4>\n
\u53c2\u8003\u6587\u732e<\/strong><\/h4>\n[1] M. Iwao, Heterocycles, 1994, 38, 45. doi: 10.3987\/COM-93-6563.<\/a><\/p>\n