{"id":1291,"date":"2014-05-29T09:04:26","date_gmt":"2014-05-29T01:04:26","guid":{"rendered":"\/\/www.gsbet888.com\/?p=1291"},"modified":"2019-08-02T18:56:54","modified_gmt":"2019-08-02T10:56:54","slug":"%e4%ba%a4%e5%8f%89%e7%be%9f%e9%86%9b%e7%bc%a9%e5%90%88%e5%8f%8d%e5%ba%94cross-aldol-reaction","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/reactions\/%e5%8a%a0%e6%88%90%e5%8f%8d%e5%ba%94\/2014\/05\/%e4%ba%a4%e5%8f%89%e7%be%9f%e9%86%9b%e7%bc%a9%e5%90%88%e5%8f%8d%e5%ba%94cross-aldol-reaction.html","title":{"rendered":"\u4ea4\u53c9\u7f9f\u919b\u7f29\u5408\u53cd\u5e94Cross Aldol Reaction"},"content":{"rendered":"
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\u6839\u636e\u70ef\u9187\u76d0\u7684\u7acb\u4f53\u5dee\u5f02\u6027\u3001\u4e0e\u7acb\u4f53\u7279\u5f02\u7684\u919b\u53ca\u916e\u53cd\u5e94\uff0c\u53ef\u76f8\u5e94\u5f97\u5230syn<\/em>\/anti<\/em>-\u7f9f\u919b\u4f53\u3002<\/p>\n \u7531\u8fc1\u79fb\u91d1\u5c5e\u5316\u53ef\u4ee5\u5236\u5907Li\u3001Na\u3001Mg\u3001Zn\u3001B\u3001Al\u3001Ti\u7b49\u5404\u79cd\u91d1\u5c5e\u70ef\u9187\u76d0\u3001\u5176\u4e2d\u53ea\u6709\u7845\u548c\u9521\u7684\u70ef\u9187\u76d0\u53ef\u4ee5\u5206\u79bb\u7cbe\u5236\u3002\u7279\u522b\u662f\u5728\u8def\u6613\u65af\u9178\u6027\u6761\u4ef6\u4e0b\u7845\u70ef\u9187\u76d0\u7684\u7f9f\u919b\u52a0\u6210\u53cd\u5e94\u901a\u5e38\u79f0\u4f5c\u5411\u5c71\u7f9f\u919b\u7f29\u5408<\/a><\/strong>\u53cd\u5e94\u3002<\/p>\n \u5728\u5168\u5408\u6210\u4e2d\uff0c\u8be5\u5076\u8054\u7f29\u5408\u7684\u4f8b\u5b50\u4e5f\u4e0d\u5c11\u3002\u5176\u4ed6\u7684\u4f8b\u5b50\u8be6\u89c1\u6587\u732e\u30fbReview\u3002<\/p>\n <\/p>\n \u30fbHeathcock, C. H.\u00a0Comprehensive Organic Synthesis<\/em>\u00a01991<\/strong>,\u00a02<\/em>, 133. <\/p>\n \u7528Zimmerman-Traxler\u516d\u5143\u73af\u8fc7\u6e21\u6001\u6a21\u578b<\/strong>(J. Am. Chem. Soc.<\/a><\/em>\u00a01957<\/strong>,\u00a079<\/em>, 1920<\/a>.)\u80fd\u591f\u8f83\u597d\u7684\u89e3\u91ca\u8bf4\u660e\u5e95\u7269\u4e0e\u4ea7\u7269\u7acb\u4f53\u5316\u5b66\u89c1\u5f97\u5173\u7cfb\u3002\u56e0\u4e3a\u919b\u7684\u53d6\u4ee3\u57faequatorial\u5904\u5728\u5e73\u4f0f\u4f4d\u7f6e\u7684\u8fc7\u6e21\u6001\u7a33\u5b9a\uff0c\u6709\u70ef\u9187\u7684\u7acb\u4f53\u7279\u5f02\u6027\u51b3\u5b9a\u4ea7\u7269\u7684\u7acb\u4f53\u5316\u5b66\u3002\u4e5f\u5c31\u662f\u8bf4\uff0c\u7531Z<\/i>-\u70ef\u9187\u76d0\u5f97\u5230syn\u6784\u578b\u7f9f\u919b\u4ea7\u7269<\/em>\u3001\u7531E<\/i>-\u70ef\u9187\u76d0\u5f97\u5230anti<\/em>\u6784\u578b<\/strong>\u4ea7\u7269\u3002 \u52a0\u5165HMPA\u7b49\u4e0e\u9502\u7b49\u91d1\u5c5e\u914d\u4f4d\u80fd\u529b\u8f83\u5f3a\u7684\u914d\u4f4d\u6027\u6eb6\u5242\u3001\u53ef\u4f7f\u91d1\u5c5e\u70ef\u9187\u76d0\u5f97\u5230\u6781\u5316\uff0c\u63d0\u9ad8\u53cd\u5e94\u6027\u80fd\u3002\u53e6\u4e00\u65b9\u9762\uff0c\u56e0\u5b83\u4e0d\u53ef\u80fd\u91c7\u53d6\u516d\u5143\u73af\u8fc7\u6e21\u6001\uff0c\u4f1a\u4f7f\u9009\u62e9\u6027\u53cd\u8f6c\uff0c\u5c31\u53d8\u5f97\u4f9d\u8d56\u4e8e\u5e95\u7269\u3002<\/p>\n <\/p>\n \u542b\u6709\u53d6\u4ee3\u57fa\u7684\u540c\u7684\u70ef\u9187\u76d0\u5236\u5907\uff0c\u4f4d\u7f6e\u9009\u62e9\u6027\u662f\u5e38\u89c1\u95ee\u9898\uff0c \u901a\u8fc7\u70ed\u529b\u5b66\/\u901f\u5ea6\u8bba\u7684\u6761\u4ef6\u63a7\u5236\u4e5f\u80fd\u5b9e\u73b0\u9ad8\u4f4d\u7f6e\u9009\u62e9\u6027\u3002<\/p>\n <\/p>\n \u787c\u7684\u70ef\u9187\u76d0B-O\u952e\u8f83\u77ed\uff0c\u80fd\u591f\u5f62\u6210\u7a33\u56fa\u7684\u516d\u5143\u73af\u3001\u76f8\u6bd4\u9502\u7684\u70ef\u9187\u76d0\u7acb\u4f53\u9009\u62e9\u6027\u4f1a\u63d0\u9ad8\u3002<\/p>\n \u787c\u7684\u70ef\u9187\u76d0\uff0c\u901a\u8fc7\u4e0d\u540c\u8bd5\u5242\u5904\u7406\u53ef\u4ee5\u9009\u62e9\u6027\u7684\u5f97\u5230E\/Z\u5f0f\u70ef\u9187\u76d0[1]\n <\/p>\n Merrilactone A\u7684\u5408\u6210[2]\uff1a\u975e\u5bfe\u79f0\u5206\u5b50\u5185\u7f9f\u919b\u53cd\u5e94\u7684\u5e94\u7528\u3002<\/p>\n <\/p>\n \u7fb0\u57fa\u5316\u5408\u7269\u7684\u5982\u679c\u4e0d\u80fd\u4ea7\u751f\u70ef\u9187\u5316\u5408\u7269(\u4f8b\u5982HCHO\u3001ArCHO\u3001Ar2<\/sub>CO\u7b49)\u3001\u5219\u5bb9\u6613\u53d1\u751f\u4ea4\u53c9\u7f9f\u919b\u53cd\u5e94\u3002(Claisen-Schmidt\u53cd\u5fdc<\/strong>) [3]\n\n
\n\u30fbKim, B. M. et al.\u00a0Comprehensive Organic Synthesis<\/em>\u00a01991<\/strong>,\u00a02<\/em>, 239.
\n\u30fbPaterson, I.\u00a0Comprehensive Organic Synthesis<\/em>\u00a01991<\/strong>,\u00a02<\/em>, 301.
\n\u30fbMahrwald, R. ed.\u00a0Modern Aldol Reactions<\/em><\/a>\u00a0Wiley-VCH,\u00a02004<\/strong>
\n\u30fbReview: Palomo, C.; Oiarbide, M.; Garcia, J. M.\u00a0Chem. Eur. J.<\/em>\u00a02002<\/strong>,\u00a08<\/em>, 36.\u00a0[abstract]<\/a>
\n\u30fbReview: Palomo, C.; Oiarbide, M.; Garcia, J. M.\u00a0Chem. Soc. Rev.<\/em>\u00a02004<\/strong>,\u00a033<\/em>, 65. DOI:10.1039\/b202901d<\/a>
\n\u30fbReview: Schetter, B.; Mahrwald, R.\u00a0Angew. Chem. Int. Ed.<\/em>\u00a02006<\/strong>,\u00a045<\/em>, 7506. doi:10.1002\/anie.200602780<\/a><\/p>\n\n
\n\u4e00\u822c\u800c\u8a00\uff0c\u4f7f\u7528M-O\u952e\u5f3a\u7684\u91d1\u5c5e\uff08\u786c\u9178\uff0c\u7edc\u5408\u80fd\u8f83\u5927\u7684\u91d1\u5c5e\uff09\u516d\u5143\u73af\u8fc7\u6e21\u6001\u7684\u73af\u8db3\u591f\u7a33\u56fa\uff0c\u7acb\u4f53\u9009\u62e9\u6027\u4f1a\u63d0\u9ad8\u3002<\/p>\n<\/a><\/p>\n
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\n[2] (a) Inoue, M.; Sato, T.; Hirama, M.\u00a0Angew. Chem. Int. Ed.<\/em>\u00a02006<\/strong>,\u00a045<\/em>, 4843. doi:10.1002\/anie.200601358<\/a>\u00a0(b) Inoue, M.; Lee, N.; Kasuya, S.; Sato, T.; Hirama, M.; Moriyama, M.; Fukuyama, Y.\u00a0J. Org. Chem.<\/em>\u00a02007<\/strong>,\u00a072<\/em>, 3065. DOI:\u00a010.1021\/jo0700474\u00a0<\/a>
\n[3] (a) Schmidt, J. G.\u00a0Ber.<\/em>\u00a01880<\/strong>,\u00a013<\/em>, 2342. (b) Claisen, L.\u00a0Ber.<\/em>\u00a01890<\/strong>,\u00a023<\/em>, 976. <\/p>\n","protected":false},"excerpt":{"rendered":"\u6982\u8981 \u5728LDA\u7b49\u5f3a\u78b1\u4e0b\uff0c\u5c06doner\u4e00\u4fa7\u7684\u7fb0\u57fa\u5316\u5408\u7269\u7684\u03b1\u4f4d\u5b8c\u5168\u8131\u6c22\u3001\u63d0\u524d\u5236\u5907\u91d1\u5c5e\u70ef\u9187\u76d0\uff0c\u6291\u5236\u5176\u81ea\u7f29\u5408\uff0c\u5f97\u5230\u4ea4\u53c9\u7f29\u5408\u4ea7\u7269\u7684\u65b9\u6cd5\u3002 \u6839\u636e\u70ef\u9187\u76d0\u7684\u7acb\u4f53\u5dee\u5f02\u6027\u3001\u4e0e\u7acb\u4f53\u7279\u5f02\u7684\u919b\u53ca\u916e\u53cd\u5e94\uff0c\u53ef\u76f8\u5e94\u5f97\u5230syn\/anti-\u7f9f\u919b\u4f53\u3002 \u7531\u8fc1\u79fb\u91d1\u5c5e\u5316\u53ef\u4ee5\u5236\u5907Li\u3001Na\u3001Mg\u3001Zn\u3001B\u3001Al\u3001Ti\u7b49\u5404\u79cd\u91d1\u5c5e\u70ef\u9187\u76d0\u3001\u5176\u4e2d\u53ea\u6709\u7845\u548c\u9521\u7684\u70ef\u9187\u76d0\u53ef\u4ee5\u5206\u79bb\u7cbe\u5236\u3002\u7279\u522b\u662f\u5728\u8def\u6613\u65af\u9178\u6027\u6761\u4ef6\u4e0b\u7845\u70ef\u9187\u76d0\u7684\u7f9f\u919b\u52a0\u6210\u53cd\u5e94\u901a\u5e38\u79f0\u4f5c\u5411\u5c71\u7f9f\u919b\u7f29\u5408\u53cd\u5e94\u3002 \u5728\u5168\u5408\u6210\u4e2d\uff0c\u8be5\u5076\u8054\u7f29\u5408\u7684\u4f8b\u5b50\u4e5f\u4e0d\u5c11\u3002\u5176\u4ed6\u7684\u4f8b\u5b50\u8be6\u89c1\u6587\u732e\u30fbReview\u3002 \u57fa\u672c\u6587\u732e \u30fbHeathcock, C. H.\u00a0Comprehensive Organic Synthesis\u00a01991,\u00a02, 133. \u30fbKim, B. M. et al.\u00a0Comprehensive Organic Synthesis\u00a01991,\u00a02, 239. \u30fbPaterson, I.\u00a0Comprehensive Organic Synthesis\u00a01991,\u00a02, 301. \u30fbMahrwald, R. ed.\u00a0Modern Aldol Reactions\u00a0Wiley-VCH,\u00a02004 \u30fbReview: Palomo, C.; Oiarbide, M.; Garcia, J. M.\u00a0Chem. Eur. J.\u00a02002,\u00a08, 36.\u00a0[abstract] \u30fbReview: Palomo, C.; Oiarbide, M.; Garcia, J. M.\u00a0Chem. Soc. Rev.\u00a02004,\u00a033, 65. DOI:10.1039\/b202901d \u30fbReview: Schetter, B.; Mahrwald, R.\u00a0Angew. Chem. Int. Ed.\u00a02006,\u00a045, 7506. doi:10.1002\/anie.200602780 \u53cd\u5e94\u673a\u7406 \u7528Zimmerman-Traxler\u516d\u5143\u73af\u8fc7\u6e21\u6001\u6a21\u578b(J. Am. Chem. Soc.\u00a01957,\u00a079, 1920.)\u80fd\u591f\u8f83\u597d\u7684\u89e3\u91ca\u8bf4\u660e\u5e95\u7269\u4e0e\u4ea7\u7269\u7acb\u4f53\u5316\u5b66\u89c1\u5f97\u5173\u7cfb\u3002\u56e0\u4e3a\u919b\u7684\u53d6\u4ee3\u57faequatorial\u5904\u5728\u5e73\u4f0f\u4f4d\u7f6e\u7684\u8fc7\u6e21\u6001\u7a33\u5b9a\uff0c\u6709\u70ef\u9187\u7684\u7acb\u4f53\u7279\u5f02\u6027\u51b3\u5b9a\u4ea7\u7269\u7684\u7acb\u4f53\u5316\u5b66\u3002\u4e5f\u5c31\u662f\u8bf4\uff0c\u7531Z-\u70ef\u9187\u76d0\u5f97\u5230syn\u6784\u578b\u7f9f\u919b\u4ea7\u7269\u3001\u7531E-\u70ef\u9187\u76d0\u5f97\u5230anti\u6784\u578b\u4ea7\u7269\u3002 \u4e00\u822c\u800c\u8a00\uff0c\u4f7f\u7528M-O\u952e\u5f3a\u7684\u91d1\u5c5e\uff08\u786c\u9178\uff0c\u7edc\u5408\u80fd\u8f83\u5927\u7684\u91d1\u5c5e\uff09\u516d\u5143\u73af\u8fc7\u6e21\u6001\u7684\u73af\u8db3\u591f\u7a33\u56fa\uff0c\u7acb\u4f53\u9009\u62e9\u6027\u4f1a\u63d0\u9ad8\u3002 \u52a0\u5165HMPA\u7b49\u4e0e\u9502\u7b49\u91d1\u5c5e\u914d\u4f4d\u80fd\u529b\u8f83\u5f3a\u7684\u914d\u4f4d\u6027\u6eb6\u5242\u3001\u53ef\u4f7f\u91d1\u5c5e\u70ef\u9187\u76d0\u5f97\u5230\u6781\u5316\uff0c\u63d0\u9ad8\u53cd\u5e94\u6027\u80fd\u3002\u53e6\u4e00\u65b9\u9762\uff0c\u56e0\u5b83\u4e0d\u53ef\u80fd\u91c7\u53d6\u516d\u5143\u73af\u8fc7\u6e21\u6001\uff0c\u4f1a\u4f7f\u9009\u62e9\u6027\u53cd\u8f6c\uff0c\u5c31\u53d8\u5f97\u4f9d\u8d56\u4e8e\u5e95\u7269\u3002 \u53cd\u5e94\u5b9e\u4f8b \u542b\u6709\u53d6\u4ee3\u57fa\u7684\u540c\u7684\u70ef\u9187\u76d0\u5236\u5907\uff0c\u4f4d\u7f6e\u9009\u62e9\u6027\u662f\u5e38\u89c1\u95ee\u9898\uff0c \u901a\u8fc7\u70ed\u529b\u5b66\/\u901f\u5ea6\u8bba\u7684\u6761\u4ef6\u63a7\u5236\u4e5f\u80fd\u5b9e\u73b0\u9ad8\u4f4d\u7f6e\u9009\u62e9\u6027\u3002 \u787c\u7684\u70ef\u9187\u76d0B-O\u952e\u8f83\u77ed\uff0c\u80fd\u591f\u5f62\u6210\u7a33\u56fa\u7684\u516d\u5143\u73af\u3001\u76f8\u6bd4\u9502\u7684\u70ef\u9187\u76d0\u7acb\u4f53\u9009\u62e9\u6027\u4f1a\u63d0\u9ad8\u3002 \u787c\u7684\u70ef\u9187\u76d0\uff0c\u901a\u8fc7\u4e0d\u540c\u8bd5\u5242\u5904\u7406\u53ef\u4ee5\u9009\u62e9\u6027\u7684\u5f97\u5230E\/Z\u5f0f\u70ef\u9187\u76d0[1] Merrilactone A\u7684\u5408\u6210[2]\uff1a\u975e\u5bfe\u79f0\u5206\u5b50\u5185\u7f9f\u919b\u53cd\u5e94\u7684\u5e94\u7528\u3002 \u7fb0\u57fa\u5316\u5408\u7269\u7684\u5982\u679c\u4e0d\u80fd\u4ea7\u751f\u70ef\u9187\u5316\u5408\u7269(\u4f8b\u5982HCHO\u3001ArCHO\u3001Ar2CO\u7b49)\u3001\u5219\u5bb9\u6613\u53d1\u751f\u4ea4\u53c9\u7f9f\u919b\u53cd\u5e94\u3002(Claisen-Schmidt\u53cd\u5fdc) [3] \u5b9e\u9a8c\u6b65\u9aa4 \u5b9e\u9a8c\u6280\u5de7 \u53c2\u8003\u6587\u732e [1] Brown, H. C.; Dhar, R. K.; Bakshi, R. K.; Pandiarajan, P. K.; Singaram, B.\u00a0J. Am. Chem. Soc.\u00a01989,111, 3441. 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