{"id":25595,"date":"2019-06-13T09:22:27","date_gmt":"2019-06-13T01:22:27","guid":{"rendered":"\/\/www.gsbet888.com\/?p=25595"},"modified":"2019-06-13T09:22:27","modified_gmt":"2019-06-13T01:22:27","slug":"shibuya%e7%83%af%e4%b8%99%e4%bd%8d%e6%b0%a7%e5%8c%96","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/reactions\/2019\/06\/shibuya%e7%83%af%e4%b8%99%e4%bd%8d%e6%b0%a7%e5%8c%96.html","title":{"rendered":"Shibuya\u70ef\u4e19\u4f4d\u6c27\u5316"},"content":{"rendered":"
Shibuya\u70ef\u4e19\u4f4d\u6c27\u5316(Shibuya allylic oxidation)\u662f\u91c7\u7528\u4e8c\u6c27\u5316\u7852\u5728\u7532\u9178\/\u4e8c\u5641\u70f7\u4f53\u7cfb\u6216\u4e8c\u6c27\u5316\u7852\/\u7532\u9178\u5728\u4e8c\u5641\u70f7\u6eb6\u5242\u4e2d\uff0c\u5bf9\u70ef\u70c3\u4e2d\u70ef\u4e19\u4f4d\u8fdb\u884c\u7684\u9009\u62e9\u6027\u6c27\u5316\uff0c\u5206\u522b\u83b7\u5f97\u76f8\u5e94\u70ef\u4e19\u9187\u7532\u9178\u916f\u53ca\u70ef\u4e19\u9187\u7684\u53cd\u5e94\u3002\u8be5\u53cd\u5e94\u7531\u65e5\u672c\u5174\u548c\u682a\u5f0f\u4f1a\u793e\u4e1c\u4eac\u7814\u7a76\u5b9e\u9a8c\u5ba4(Tokyo Research Laboratories, Kowa Company, Ltd)\u7684\u6da9\u8c37\u516c\u5e78(\u6e0b\u8c37\u516c\u5e78\uff0c<\/a>Shibuya Kimiyuki)\u57281994\u5e74\u9996\u6b21\u62a5\u9053\u3002\u5177\u6709\u4f18\u826f\u7684\u533a\u57df\u53ca\u7acb\u4f53\u9009\u62e9\u6027\uff0c\u5c24\u5176\u9002\u7528\u4e8e\u5177\u6709\u8f83\u5927\u7acb\u4f53\u4f4d\u963b\u7684\u70ef\u70c3\u5e95\u7269\u3002\u76ee\u524d\uff0c\u5df2\u7ecf\u5e7f\u6cdb\u5e94\u7528\u4e8e\u5404\u7c7b\u5929\u7136\u4ea7\u7269\u5168\u5408\u6210\u7684\u5173\u952e\u6b65\u9aa4\u3002 (+)-ingenol\u7684\u5168\u5408\u6210[1] (+)-upial\u7684\u5168\u5408\u6210[2]\n (\u00b1)-erysotramidine\u7684\u5168\u5408\u6210[3][4]\n \u4e8c\u6c27\u5316\u7852\u5728\u7532\u9178\/<\/strong>\u4e8c\u5641\u70f7\u4f53\u7cfb\u4e2d\u7684\u6c27\u5316<\/strong><\/p>\n \u5411\u70ef\u70c3\u5e95\u7269(1 eq.)\u7684\u4e59\u919a\u6eb6\u6db2(\u7ef4\u6301\u5e95\u7269\u6d53\u5ea6\u4e3a1M)\u4e2d\u52a0\u5165\u5e72\u71e5\u7684\u4e8c\u5641\u70f7\uff0c\u968f\u540e\u52a0\u5165\u4e8c\u6c27\u5316\u7852(2eq.)\u53ca\u7532\u9178(\u7ef4\u6301\u4e0e\u4e8c\u5641\u70f7\u4f53\u79ef\u6bd4\u4e3a1:2v\/v)\uff0c\u5c06\u4e0a\u8ff0\u53cd\u5e94\u6df7\u5408\u7269\u572860\u00b0C\u4e0b\u6405\u62cc\u52a0\u70ed\uff0c\u76f4\u81f3\u53cd\u5e94\u7ed3\u675f\u3002\u53cd\u5e94\u7ed3\u675f\u540e\uff0c\u5c06\u53cd\u5e94\u6db2\u52a0\u5165\u6c34\/\u4e59\u919a(2 :1 v\/v)\u8fdb\u884c\u7a00\u91ca\uff0c\u901a\u8fc7\u7845\u85fb\u571f\u8fc7\u6ee4\u9664\u53bb\u4e0d\u6eb6\u7269\uff0c\u5e76\u5206\u79bb\u51fa\u6709\u673a\u76f8\u3002\u6c34\u76f8\u7ee7\u7eed\u7528\u4e59\u919a\u8403\u53d6\u4e09\u6b21\uff0c\u5408\u5e76\u6709\u673a\u76f8\uff0c\u5c06\u6709\u673a\u76f8\u4f9d\u6b21\u7528\u6c34\u3001\u9971\u548c\u78b3\u9178\u6c22\u94a0\u53ca\u9971\u548c\u98df\u76d0\u6c34\u6d17\u6da4\uff0c\u6700\u540e\u91c7\u7528\u65e0\u6c34\u786b\u9178\u9541\u8fdb\u884c\u5e72\u71e5\u3002\u51cf\u538b\u9664\u53bb\u6eb6\u5242\uff0c\u6b8b\u4f59\u7269\u91c7\u7528\u7845\u80f6\u67f1\u8272\u8c31 (Et2<\/sub>O\/\u6b63\u5df1\u70f71 : 5 v\/v\u4f5c\u4e3a\u6d17\u8131\u5242)\u5206\u79bb\u7eaf\u5316\uff0c\u83b7\u5f97\u76f8\u5e94\u76ee\u6807\u4ea7\u7269\u3002<\/p>\n \u4e8c\u6c27\u5316\u7852\/<\/strong>\u7532\u9178\u5728\u4e8c\u5641\u70f7\u6eb6\u5242\u4e2d\u7684\u6c27\u5316<\/strong><\/p>\n \u5c06\u4e8c\u6c27\u5316\u7852(1.1 eq.)\u60ac\u6d6e\u4e8e\u5e72\u71e5\u7684\u4e8c\u5641\u70f7\u4e2d\uff0c\u52a0\u5165\u7532\u9178(1 eq.)\u3002\u6405\u62cc5 min\u540e\uff0c\u518d\u52a0\u5165\u70ef\u70c3\u5e95\u7269(1 eq.)\u7684\u4e8c\u5641\u70f7\u6eb6\u6db2(\u7ef4\u6301\u5e95\u7269\u6d53\u5ea61M)\u3002\u5c06\u4e0a\u8ff0\u53cd\u5e94\u6df7\u5408\u7269\u572860\u00b0C\u4e0b\u6405\u62cc\u52a0\u70ed\uff0c\u76f4\u81f3\u53cd\u5e94\u7ed3\u675f\u3002\u53cd\u5e94\u7ed3\u675f\u540e\uff0c\u5c06\u53cd\u5e94\u6db2\u52a0\u5165\u6c34\/\u4e59\u919a(2 :1 v\/v)\u8fdb\u884c\u7a00\u91ca\uff0c\u5e76\u52a0\u5165\u78b3\u9178\u6c22\u94a0\u8fdb\u884c\u4e2d\u548c\u3002\u901a\u8fc7\u7845\u85fb\u571f\u8fc7\u6ee4\u9664\u53bb\u4e0d\u6eb6\u7269\uff0c\u5e76\u5206\u79bb\u51fa\u6709\u673a\u76f8\u3002\u6c34\u76f8\u7ee7\u7eed\u7528\u4e59\u919a\u8403\u53d6\u4e09\u6b21\uff0c\u5408\u5e76\u6709\u673a\u76f8\uff0c\u5c06\u6709\u673a\u76f8\u7528\u9971\u548c\u98df\u76d0\u6c34\u6d17\u6da4\uff0c\u6700\u540e\u91c7\u7528\u65e0\u6c34\u786b\u9178\u9541\u8fdb\u884c\u5e72\u71e5\u3002\u51cf\u538b\u9664\u53bb\u6eb6\u5242\uff0c\u6b8b\u4f59\u7269\u91c7\u7528\u7845\u80f6\u67f1\u8272\u8c31(\u4f9d\u6b21\u91c7\u7528\u6b63\u5df1\u70f7\u53caEt2<\/sub>O\/\u6b63\u5df1\u70f71 : 20 v\/v\u4f5c\u4e3a\u6d17\u8131\u5242\u8fdb\u884c\u68af\u5ea6\u6d17\u8131)\u5206\u79bb\u7eaf\u5316\uff0c\u83b7\u5f97\u76f8\u5e94\u76ee\u6807\u4ea7\u7269\u3002<\/p>\n \u5c0f\u7f16\u90d1\u91cd\u63d0\u793a\uff1a\u7532\u9178\u5177\u6709\u8f83\u5f3a\u8150\u8680\u6027\u53ca\u76ae\u80a4\u523a\u6fc0\u6027\uff0c\u540c\u65f6\u4e8c\u6c27\u5316\u7852\u6709\u5267\u6bd2\u53ca\u81f4\u764c\u6027\uff0c\u4f7f\u7528\u65f6\u9700\u8981\u7279\u522b\u4ed4\u7ec6\uff0c\u7a7f\u6234SSG (Silver Shield Gloves)<\/strong>\u3001\u9632\u5316\u670d\u53ca\u62a4\u76ee\u955c\uff0c\u5e76\u5728\u901a\u98ce\u6a71\u5185\u5c0f\u5fc3\u64cd\u4f5c\u3002<\/strong><\/p>\n <\/p>\n<\/a><\/p>\n
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\u57fa\u672c\u6587\u732e<\/strong><\/h4>\n[1] K. Shibuya, Synth. Commun. 1994, 24, 2923.doi:10.1080\/00397919408010614.<\/a><\/p>\n
\u53cd\u5e94\u673a\u7406<\/strong><\/h4>\n
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\u5b9e\u9a8c\u6b65\u9aa4<\/strong><\/h4>\n
\u5b9e\u9a8c\u5b89\u5168\u987b\u77e5<\/strong><\/h4>\n
\u53c2\u8003\u6587\u732e<\/strong><\/h4>\n
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