{"id":15952,"date":"2017-11-02T06:05:09","date_gmt":"2017-11-01T22:05:09","guid":{"rendered":"\/\/www.gsbet888.com\/?p=15952"},"modified":"2019-08-02T18:52:40","modified_gmt":"2019-08-02T10:52:40","slug":"tamaru-mori-%e5%8f%8d%e5%ba%94","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/reactions\/%e5%8a%a0%e6%88%90%e5%8f%8d%e5%ba%94\/2017\/11\/tamaru-mori-%e5%8f%8d%e5%ba%94.html","title":{"rendered":"Tamaru-Mori \u53cd\u5e94"},"content":{"rendered":"
Tamaru-Mori \u53cd\u5e94(Tamaru-Mori reaction)\u662f\u5728\u954d\u50ac\u5316\u5242\u4e0e\u4e09\u4e59\u57fa\u787c\u4f5c\u7528\u4e0b\uff0c\u919b\u4e0e1,3-\u4e8c\u70ef\u95f4\u8fdb\u884c\u7684\u5177\u6709\u9ad8\u5ea6\u7acb\u4f53\u4e0e\u533a\u57df\u9009\u62e9\u6027\u7684\u9ad8\u70ef\u4e19\u57fa\u5316\u53cd\u5e94[1]<\/sup>\u3002<\/p>\n \u8be5\u53cd\u5e94\u57281998\u5e74\u7531\u65e5\u672c\u957f\u5d0e\u5927\u5b66(Nakasaki University)\u7684\u7530\u4e38\u826f\u76f4\u7814\u7a76\u7ec4(Tamaru Yoshinao)\u57281998\u5e74\u9996\u6b21\u62a5\u9053[1]-[3]<\/sup>\u3002<\/p>\n 2006\u5e74\u7530\u4e38\u826f\u76f4(Tamaru Yoshinao)\u4e0e\u68ee\u6b63\u5f66(Mori Masahiko)\u91c7\u7528\u4e8c\u4e59\u57fa\u950c\u4ee3\u66ff\u4e09\u4e59\u57fa\u787c\uff0c\u5c06\u5e95\u7269\u8303\u56f4\u6269\u5c55\u81f3\u7acb\u4f53\u4f4d\u963b\u8f83\u5927\u7684\u8102\u80aa\u919b\u3001\u916e\u53ca1,3-\u73af\u5df1\u4e8c\u70ef[4]<\/sup>\u3002<\/p>\n \u542b\u6c2e\u6742\u73af\u7684\u5408\u6210[1]\n Amphidinolide C \u4e2dC1-C9\u7247\u6bb5\u7684\u6784\u5efa[2] [3]\n \u919b\u4e9a\u80fa\u7684\u9ad8\u70ef\u4e19\u57fa\u5316[5] [6]\n \u5206\u5b50\u5185Tamaru-Mori \u53cd\u5e94[7]\n Et3<\/sub>B<\/strong>:<\/strong>\u7528\u6ce8\u5c04\u5668\u5411\u5df2\u5145\u5165N2<\/sub>\uff0c\u5e76\u88c5\u6709Ni(acac)2<\/sub> (0.01eq.) \u7684\u70e7\u74f6\u4e2d\u52a0\u5165\u5e72\u71e5\u7684THF (\u7ef4\u6301\u5e95\u7269\u6d53\u5ea6\u4e3a1.6 M)\uff0c1,3-\u4e8c\u70ef(4 eq.)\u3001\u919b(1eq.)\u53caEt3<\/sub>B (2.4 eq.)\u3002\u5c06\u4e0a\u8ff0\u5747\u76f8\u6df7\u5408\u7269\u5728\u5ba4\u6e29\u4e0b\u6405\u62cc\uff0c\u5e76\u901a\u8fc7GLC\u4e0eTLC\u76d1\u63a7(\u6b63\u5df1\u70f7\/\u4e59\u9178\u4e59\u916f4\/1 v\/v)\u76f4\u81f3\u53cd\u5e94\u7ed3\u675f\u3002\u53cd\u5e94\u7ed3\u675f\u540e\uff0c\u5c06\u53cd\u5e94\u6db2\u7528\u4e59\u9178\u4e59\u916f\u8fdb\u884c\u7a00\u91ca\uff0c\u518d\u4f9d\u6b21\u75282 M HCl\u3001\u9971\u548cNaHCO3<\/sub>\u6eb6\u6db2\u53ca\u9971\u548cNaCl\u6eb6\u6db2\u6d17\u6da4\uff0c\u5e76\u7528\u65e0\u6c34MgSO4<\/sub>\u8fdb\u884c\u5e72\u71e5\uff0c\u6700\u540e\u51cf\u538b\u9664\u53bb\u6eb6\u5242\u3002\u5c06\u7c97\u4ea7\u7269\u91c7\u7528\u7845\u80f6\u67f1\u8272\u8c31(\u6b63\u5df1\u70f7\/\u4e59\u9178\u4e59\u916f16\/1 v\/v)\u5206\u79bb\u7eaf\u5316\u540e\uff0c\u83b7\u5f97\u76f8\u5e94\u9ad8\u70ef\u4e19\u9187\u4ea7\u7269\u3002<\/p>\n Et2<\/sub>Zn:<\/strong><\/p>\n N2<\/sub>\u6c14\u6c1b\u4e0b\uff0c\u7528\u6ce8\u5c04\u5668\u5411\u88c5\u6709Ni(acac)2<\/sub>(0.1 eq.)\u7684\u70e7\u74f6\u4e2d\u52a0\u5165\u65e0\u6c34THF (\u7ef4\u6301\u5e95\u7269\u6d53\u5ea6\u4e3a0.2 M)\uff0c\u968f\u540e\u4f9d\u6b21\u52a0\u51651,3-\u4e8c\u70ef (4 eq.)\u3001\u919b(1eq.)\u53caEt2<\/sub>Zn (2.4 eq.)\u3002\u5c06\u4e0a\u8ff0\u53cd\u5e94\u6df7\u5408\u7269\u5728\u5ba4\u6e29\u4e0b\u6405\u62cc30 min\u540e\uff0c\u52a0\u51652 M HCl\u8fdb\u884c\u6dec\u706d\u3002\u5145\u5206\u6dec\u706d\u540e\uff0c\u91c7\u7528\u4e59\u9178\u4e59\u916f\u8fdb\u884c\u8403\u53d6\uff0c\u5c06\u5408\u5e76\u7684\u6709\u673a\u76f8\u7528\u9971\u548cNaCl\u6eb6\u6db2\u6d17\u6da4\uff0c\u5e76\u7528\u65e0\u6c34MgSO4<\/sub>\u8fdb\u884c\u5e72\u71e5\uff0c\u6700\u540e\u51cf\u538b\u9664\u53bb\u6eb6\u5242\u3002\u5c06\u7c97\u4ea7\u7269\u91c7\u7528\u7845\u80f6\u67f1\u8272\u8c31(\u6b63\u5df1\u70f7\/\u4e59\u9178\u4e59\u916f16\/1 v\/v)\u5206\u79bb\u7eaf\u5316\u540e\uff0c\u83b7\u5f97\u76f8\u5e94\u9ad8\u70ef\u4e19\u9187\u4ea7\u7269\u3002<\/p>\n \u2460<\/strong>\u4e8c\u4e59\u57fa\u950c\u4e0e\u4e09\u4e59\u57fa\u787c\u6781\u6613\u81ea\u71c3\uff0c\u53d6\u7528\u65f6\u9700\u8981\u5728\u6c29\u6c14\u624b\u5957\u7bb1\u5185\u8fdb\u884c\u3002<\/strong> <\/p>\n<\/a><\/p>\n
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\u57fa\u672c\u6587\u732e<\/strong><\/h4>\n[1] M. Kimura, A. Ezoe, K. Shibata, Y. Tamaru, J. Am. Chem. Soc. 1998, 120, 4033. doi: 10.1021\/ja973847c. <\/a><\/p>\n[2] M. Kimura, H. Fujimatsu, A. Ezoe, K. Shibata, M. Shimizu, S. Matsumoto, Y. Tamaru. Angew. Chem. Int. Ed. 1999, 38, 397. doi: 10.1002\/(SICI)1521-3773(19990201)38:3<397::AID-ANIE397>3.0.CO;2-Y.<\/a><\/p>\n[3] M. Kimura, A. Ezoe, S. Tanaka, Y. Tamaru, Angew. Chem. Int. Ed.\u00a02001,\u00a040, 3600. doi:10.1002\/1521-3773(20011001)40:19<3600::AID-ANIE3600>3.0.CO;2-N. <\/a><\/p>\n[4] M. Kimura, A. Ezoe, M. Mori, K. Iwata,Y. Tamaru, J. Am. Chem. Soc. 2006, 128, 8559. doi: 10.1021\/ja0608904.<\/a><\/p>\n
\u53cd\u5e94\u673a\u7406<\/strong><\/h4>\n
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\u53cd\u5e94\u5b9e\u4f8b<\/strong><\/h4>\n
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\u5b9e\u9a8c\u6b65\u9aa4<\/strong><\/h4>\n
\u5b9e\u9a8c\u5b9e\u9a8c\u5b89\u5168\u987b\u77e5<\/strong><\/h4>\n
\n<\/strong>\u2461<\/strong>\u53cc<\/strong>(<\/strong>\u4e59\u9170\u4e19\u916e<\/strong>)<\/strong>\u5408\u954d<\/strong>(II)<\/strong>\u4e3a\u53ef\u7591\u81f4\u764c\u7269\uff0c\u4f7f\u7528\u65f6\u9700\u8981\u5341\u5206\u5c0f\u5fc3\u3002<\/strong><\/p>\n\u53c2\u8003\u6587\u732e<\/strong><\/h4>\n[1] M. Kimura<\/a>, A. Ezoe<\/a>, M. Mori<\/a>, Y. Tamaru<\/a>, J. Am. Chem. Soc.\u00a02005,\u00a0127, 201. doi: 10.1021\/ja0469030.<\/a><\/p>\n[2] M. Kimura, Org. Synth.\u00a02013,\u00a090, 105. doi: 10.15227\/orgsyn.090.0105.<\/a><\/p>\n[3] M. P. Paudyal, N. P. Rath, C. D. Spilling, Org. Lett. 2010, 12, 2954. doi: 10.1021\/ol100959a.<\/a><\/p>\n[4] Y. Tamaru, M. Kimura, Org. Synth. 2006,\u00a083, 88. doi: 10.15227\/orgsyn.083.0088.<\/a><\/p>\n[5] M. Kimura, A. Miyachi, K. Kojima, S. Tanaka, Y. Tamaru,\u00a0J. Am. Chem. Soc.\u00a02004,\u00a0126, 14360. doi: 10.1021\/ja0450354.<\/a><\/p>\n[6] M. Kimura, A. Ezoe, S. Tanaka, Y. Tamaru, Angew. Chem. Int. Ed.\u00a02001,\u00a040, 3600. doi: 10.1002\/1521-3773(20011001)40:19<3600::AID-ANIE3600>3.0.CO;2-N. <\/a><\/p>\n[7] K. Shibata, M. Kimura, M. Shimizu, Y. Tamaru,\u00a0Org. Lett.\u00a02001,\u00a03, 2181. doi: 10.1021\/ol0100879.<\/a><\/p>\n