{"id":29595,"date":"2019-11-29T08:00:43","date_gmt":"2019-11-29T00:00:43","guid":{"rendered":"\/\/www.gsbet888.com\/?p=29595"},"modified":"2019-11-27T22:38:23","modified_gmt":"2019-11-27T14:38:23","slug":"murahashi%e5%81%b6%e8%81%94%e5%8f%8d%e5%ba%94","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/reactions\/2019\/11\/murahashi%e5%81%b6%e8%81%94%e5%8f%8d%e5%ba%94.html","title":{"rendered":"Murahashi\u5076\u8054\u53cd\u5e94"},"content":{"rendered":"

\u6982\u8981<\/strong><\/h4>\n
1975\u5e74\uff0c\u65e5\u672c\u5927\u962a\u5927\u5b66\u5e94\u7528\u5316\u5b66\u7cfb\u5de5\u5b66\u9662 (\u5927\u962a\u5927\u5b66\u5de5\u5b66\u90e8\u5fdc\u7528\u7cbe\u5bc6\u5316\u5b66\u79d1, Department of Applied Chemistry, Faculty of Engineering, Osaka University)\u7684\u6751\u6865\u4fca\u4e00 (\u6751\u6a4b \u4fca\u4e00, Murahashi Shun-ichi)\u7814\u7a76\u5ba4\u62a5\u9053\u4e86\u94af\u50ac\u5316\u5242\u91c7\u7528\u7684\u5364\u4ee3\u70ef\u70c3\u4e0e\u70f7\u57fa\u9502\u8bd5\u5242\u8fdb\u884c\u7684\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\uff0c\u7814\u7a76\u53d1\u73b0\u53cd\u5e94\u5177\u6709\u4f18\u826f\u7684\u7acb\u4f53\u9009\u62e9\u6027\uff0c\u5364\u4ee3\u70ef\u70c3\u6784\u578b\u5b8c\u5168\u4fdd\u6301^{[1]<\/sup>\u3002<\/p>\n}
$\"\"$ <\/a><\/p>\n
1979\u5e74\uff0cMurahashi\u8fdb\u4e00\u6b65\u5c06\u9502\u8bd5\u5242\u6269\u5c55\u81f3\u82b3\u57fa\u4e0e\u6742\u82b3\u57fa\u9502\uff0c\u5e76\u5c06\u5e95\u7269\u6269\u5c55\u81f3\u4e0e\u82b3\u57fa\u5171\u8f6d\u7684\u5364\u4ee3\u70ef^{[2]<\/sup>\uff0c\u540c\u6837\u5177\u6709\u4f18\u826f\u7684\u7acb\u4f53\u9009\u62e9\u6027\u3002<\/p>\n}
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1982\u5e74\uff0cG. Linstrumelle\u5c06\u8be5\u53cd\u5e94\u6761\u4ef6\u5e94\u7528\u4e8e\u8054\u70ef\u57fa\u9502\uff0c\u6210\u529f\u5b9e\u73b0\u8054\u70ef\u57fa\u9502\u7684\u4e59\u70ef\u57fa\u5316\u4e0e\u82b3\u57fa\u5316^{[3]-[4]<\/sup>\u3002<\/p>\n}
$\"\"$ <\/a><\/p>\n
1987\u5e74\uff0cPelter\u6210\u529f\u5c06Murahashi\u7684\u53cd\u5e94\u6761\u4ef6\u6269\u5c55\u81f3\u82c4\u57fa\u4e0e\u8089\u6842\u57fa\u5364\u4ee3\u70f7^{[5]<\/sup>\uff0c\u5e76\u83b7\u5f97\u826f\u597d\u7684\u4ea7\u7387\u3002<\/p>\n}
$\"\"$ <\/a><\/p>\n
\u867d\u7136\u4e0a\u8ff0\u53cd\u5e94\u6761\u4ef6\u5177\u6709\u5e7f\u6cdb\u7684\u5e95\u7269\u9002\u7528\u8303\u56f4\u4e0e\u8f83\u9ad8\u7684\u4ea7\u7387\u3002\u7136\u800c\uff0c\u90e8\u5206\u5e95\u7269\u5728\u8be5\u6761\u4ef6\u4e0b\u53cd\u5e94\u8f83\u6162\uff0c\u9700\u8981\u8f83\u9ad8\u7684\u6e29\u5ea6\u3001\u8fc7\u91cf\u7684\u6709\u673a\u9502\u8bd5\u5242\u53ca\u8f83\u957f\u7684\u53cd\u5e94\u65f6\u95f4\u3002\u540c\u65f6\uff0c\u7531\u4e8e\u9502\u8bd5\u5242\u8f83\u9ad8\u7684\u53cd\u5e94\u6d3b\u6027\uff0c\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u8fd8\u4f1a\u51fa\u73b0\u5364\u4ee3\u70c3\u4e4b\u95f4\u7684\u540c\u5076\u8054\u526f\u53cd\u5e94\u53ca\u9502-\u5364\u7d20\u4ea4\u6362\u8fc7\u7a0b\u5feb\u4e8e\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\u7684\u95ee\u9898\u3002\u56e0\u6b64\uff0c\u65e0\u6cd5\u9002\u5e94\u5927\u89c4\u6a21\u7684\u5b9e\u9a8c\u5ba4\u5408\u6210\u7814\u7a76\u53ca\u5de5\u4e1a\u751f\u4ea7\u30022010\u5e74\uff0cYoshida\u8bfe\u9898\u7ec4\u91c7\u7528\u6d41\u52a8\u578b\u5fae\u53cd\u5e94\u5668 (flow microreactor)\u5c06Li-Br\u4ea4\u6362\u4e0eMurahashi\u5076\u8054\u6210\u529f\u7ed3\u5408\uff0c\u987a\u5229\u5b8c\u6210\u4e86\u4e24\u79cd\u4e0d\u540c\u82b3\u5364\u95f4\u7684\u4ea4\u53c9\u5076\u8054\uff0c\u83b7\u5f97\u8f83\u9ad8\u7684\u4ea7\u7387\uff0c\u5e76\u4f7f\u53cd\u5e94\u65f6\u95f4\u6781\u5927\u7f29\u77ed^{[6]<\/sup>\u3002\u540c\u65f6\uff0c\u6709\u6548\u907f\u514d\u4e86\u540c\u79cd\u82b3\u5364\u95f4\u7684\u540c\u5076\u8054\u53cd\u5e94\u3002<\/p>\n}
$\"\"$ <\/a><\/p>\n
2013\u5e74\uff0cFeringa\u91c7\u7528\u53cc(\u4e09\u53d4\u4e01\u57fa\u81a6)\u5408\u94af(II)\u6216Pd-PEPPSI-IPent\u3001Pd_{2<\/sub>(dba)_{3<\/sub>\/\u4e09\u53d4\u4e01\u57fa\u81a6\u53caPd_{2<\/sub>(dba)_{3<\/sub>\/XPhos\u50ac\u5316\u5242\uff0c\u6210\u529f\u5c06\u5e95\u7269\u8303\u56f4\u6269\u5c55\u81f3\u66f4\u591a\u7684\u82b3\u5364\u53ca\u7a20\u73af\u82b3\u5364\uff0c\u53cd\u5e94\u6761\u4ef6\u6e29\u548c\uff0c\u53cd\u5e94\u65f6\u95f4\u6709\u6548\u7f29\u77ed\uff0c\u540c\u6837\u907f\u514d\u4e86\u9502-\u5364\u7d20\u4ea4\u6362\u53ca\u540c\u5076\u8054\u7b49\u526f\u53cd\u5e94\u3002\u5177\u6709\u66f4\u4e3a\u5e7f\u6cdb\u7684\u5e95\u7269\u9002\u7528\u8303\u56f4\u53ca\u4f18\u826f\u7684\u53cd\u5e94\u9009\u62e9\u6027\u4e0e\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\uff0c\u751a\u81f3\u8fde\u63a5\u6709\u5bb9\u6613\u4e0e\u9502\u8bd5\u5242\u53d1\u751f\u4eb2\u6838\u53cd\u5e94\u7684\u916e\u7fb0\u57fa\u3001\u6c30\u57fa\u53ca\u70f7\u6c27\u7fb0\u57fa\u5b98\u80fd\u56e2\u76f8\u5173\u7684\u5e95\u7269\uff0c\u5747\u53ef\u5728\u8be5\u6761\u4ef6\u4e0b\u987a\u5229\u5b8c\u6210\u76f8\u5e94\u7684\u4ea4\u53c9\u5076\u8054^{[7]-[8]<\/sup>\u3002<\/p>\n}}}}}
$\"\"$ <\/a><\/p>\n
\u4e4b\u540e\uff0cMori\u91c7\u7528Ni(II)-NHC\u50ac\u5316\u5242\uff0c\u5b9e\u73b0\u4e86Murahashi\u5076\u8054\u805a\u5408 (Murahashicoupling polymerization)\uff0c\u5c06\u8be5\u53cd\u5e94\u6210\u529f\u5e94\u7528\u4e8e\u03c0-\u5171\u8f6d\u805a\u5408\u7269 (\u03c0-conjugatedpolymers)\u7684\u5408\u6210^{[9]<\/sup>\u3002<\/p>\n}
$\"\"$ <\/a><\/p>\n
2019\u5e74\uff0cFeringa\u4e0eOrgan\u5728\u6df1\u51b7\u6e29\u5ea6\u4e0b (cryogenic temperatures)\u4e0b\uff0c\u91c7\u7528\u53cd\u5e94\u6d3b\u6027\u66f4\u9ad8\u7684Pd-NHC\u50ac\u5316\u5242\uff0c\u901a\u8fc7\u6e29\u5ea6\u4f9d\u8d56\u7684\u5316\u5b66\u9009\u62e9\u6027\u5f15\u53d1\u7b56\u7565 (temperature-dependent chemoselectivity trigger)\uff0c\u6210\u529f\u5b9e\u73b0\u6c2f\u4ee3\u82b3\u57fa\u6eb4 (\u82b3\u57fa\u6c2f\u5728\u8be5\u6761\u4ef6\u4e0b\u65e0\u6cd5\u53c2\u4e0e\u5076\u8054\u8fc7\u7a0b)\u7684\u5316\u5b66\u9009\u62e9\u6027\u4ea4\u53c9\u5076\u8054^{[10]<\/sup>\u3002\u540c\u65f6\uff0c\u7814\u7a76\u53d1\u73b0\u542b\u6709\u82b3\u57fa\u6c2f\u5b98\u80fd\u56e2\u7684\u5076\u8054\u4ea7\u7269\u53ef\u4ee5\u5728\u4e00\u9505\u6761\u4ef6\u4e0b\u5b8c\u6210\u591a\u79cd\u540e\u7eed\u7684\u4e8c\u7ea7\u5076\u8054\u8fc7\u7a0b\uff0c\u5982Suzuki-Miyaura\u53cd\u5e94\u3001Negishi\u53cd\u5e94\u53caBuchwald-Hartwig\u53cd\u5e94\u7b49\u3002<\/p>\n}
$\"\"$ <\/a><\/p>\n
\u6587\u732e\u4e2d\u5c06\u4e0a\u8ff0\u94af\u50ac\u5316\u7684\u5364\u4ee3\u70c3\u4e0e\u6709\u673a\u9502\u8bd5\u5242\u4e4b\u95f4\u7684\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\u79f0\u4e3aMurahashi\u5076\u8054\u53cd\u5e94 (Murahashi coupling)\u6216Murahashi\u4ea4\u53c9\u5076\u8054\u53cd\u5e94 (Murahashi cross-coupling)\u3002\u8be5\u53cd\u5e94\u5177\u6709\u5e7f\u6cdb\u7684\u5e95\u7269\u9002\u7528\u8303\u56f4\uff0c\u4f18\u826f\u7684\u5316\u5b66\u9009\u62e9\u6027\u4e0e\u7acb\u4f53\u9009\u62e9\u6027\u53ca\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u3002\u76ee\u524d\uff0cMurahashi\u5076\u8054\u53cd\u5e94\u5728\u6709\u673a\u5408\u6210\u65b9\u6cd5\u5b66\u7814\u7a76\u3001\u533b\u836f\u53ca\u6709\u673a\u6750\u6599\u7814\u7a76\u9886\u57df\u5177\u6709\u6781\u4e3a\u5e7f\u6cdb\u7684\u5e94\u7528\u524d\u666f\u3002<\/p>\n
\u57fa\u672c\u6587\u732e<\/strong><\/h4>\n\n
[1] M. Yamamura, I. Moritani, S. Murahashi, J. Organomet. Chem<\/em>. 1975<\/strong>, 91<\/em>, C39. doi: 10.1016\/S0022-328X(00)89636-9<\/a>.<\/li>\n
[2] S. Murahashi, M. Yamamura, K. Yanagisawa, N. Mita, K. Kondo, J. Org. Chem<\/em>. 1979<\/strong>, 44<\/em>, 2408. doi: 10.1021\/jo01328a016<\/a>.<\/li>\n
[3] T. Jeffery-Luong, G. Linstrumelle, Synthesis<\/em> 1982<\/strong>, 738. doi: 10.1055\/s-1982-29923.<\/a><\/li>\n
[4] S. Murahashi, J. Organomet. Chem<\/em>. 2002<\/strong>, 653<\/em>, 27. doi: 10.1016\/S0022-328X(02)01167-1<\/a>.<\/li>\n
[5] A. Pelter, M. Rowlands, G. Clements, Synthesis<\/em> 1987<\/strong>, 51. doi: 10.1055\/s-1987-27840.<\/a><\/li>\n
[6] A. Nagaki, A.Kenmoku, Y. Moriwaki, A. Hayashi, J. Yoshida, Angew. Chem. Int. Ed. <\/em>2010<\/strong>,<\/em> *49<\/em>, 7543. doi:**10.1002\/anie.201002763<\/a>.<\/li>\n*
[7] M. Giannerini, M. Fa\u00f1an\u00e1s-Mastral, B. L. Feringa, Nat. Chem<\/em>. 2013<\/strong>, 5<\/em>, 667. doi: 10.1038\/nchem.1678<\/a>.<\/li>\n
[8] V. Hornillos, M. Giannerini, C. Vila, M. Fa\u00f1an\u00e1s-Mastral, B. L. Feringa, Org. Lett.<\/em> 2013<\/strong>, 15<\/em>, 5114. doi: 10.1021\/ol402408v<\/a>.<\/li>\n
[9] K. Fuji, S. Tamba, K. Shono, A. Sugie, A. Mori, J. Am. Chem. Soc<\/em>.\u00a02013<\/strong>, 135<\/em>, 12208. doi: 10.1021\/ja406374t<\/a>.<\/li>\n
[10] N. Sinha, D. Heijnen, B. L. Feringa, M. G. Organ, Chem. Eur. J<\/em>. 2019<\/strong>, 25<\/em>, 9180. doi: 10.1002\/chem.201901678<\/a>.<\/li>\n<\/ul>\n
\u53cd\u5e94\u673a\u7406<\/strong><\/h4>\n
\u70ef\u57fa\u5364\u53c2\u4e0e\u7684<\/strong>Murahashi<\/strong>\u5076\u8054<\/strong><\/p>\n
$\"\"$ <\/a><\/p>\n
\u82b3\u5364\u53c2\u4e0e\u7684<\/strong>Murahashi<\/strong>\u5076\u8054<\/strong><\/p>\n
$\"\"$ <\/a><\/p>\n
\u53c2\u8003\u6587\u732e<\/strong><\/h4>\n\n
[1] S. Murahashi, M. Yamamura, K. Yanagisawa, N. Mita, K. Kondo, J. Org. Chem<\/em>. 1979<\/strong>, *44,<\/em> 2408. doi:**10.1021\/jo01328a016<\/a>.<\/li>\n*
[2] M. K. Loar, J. K. Stille, J. Am. Chem. Soc<\/em>. 1981<\/strong>, 103<\/em>, 4174. doi: 10.1021\/ja00404a033<\/a>.<\/li>\n
[3] C. Amatore, A. Jutland, A. Suarez, J. Am. Chem. Soc<\/em>. 1993<\/strong>, 115<\/em>, 9531. doi: 10.1021\/ja00074a018<\/a>.<\/li>\n
[4] C. Amatore, M. Azzabi, A. Jutland, J. Am. Chem. Soc.<\/em> 1991<\/strong>, 113<\/em>, 8375. doi: 10.1021\/ja00022a026<\/a>.<\/li>\n<\/ul>\n
\u53cd\u5e94\u5b9e\u4f8b<\/strong><\/h4>\n
S1P5\u9009\u62e9\u6027\u62ee\u6297\u5242\u5173\u952e\u4e2d\u95f4\u4f53\u7684\u5408\u6210[1]\n
$\"\"$ <\/a><\/p>\n
\u8054\u82b3\u7684\u5408\u6210[2]\n
$\"\"$ <\/a><\/p>\n
Murahashi\u5076\u8054\u805a\u5408[3]\n
$\"\"$ <\/a><\/p>\n
\u5b9e\u9a8c\u6b65\u9aa4<\/strong><\/h4>\n
\u5728\u6c29\u6c14\u6c14\u6c1b\u4e0b\uff0c\u5411\u5e72\u71e5\u7684Schlenk\u74f6\u5185\u52a0\u5165Pd(P^{t<\/sup>Bu_{3<\/sub>)_{2<\/sub> (0.05 eq.)\u4e0e\u5364\u4ee3\u70c3 (1 eq.)\uff0c\u4e4b\u540e\u52a0\u5165\u65e0\u6c34\u7532\u82ef\u6eb6\u89e3 (\u7ef4\u6301\u5e95\u7269\u6d53\u5ea6\u4e3a0.15 M)\u3002\u518d\u5c06\u6709\u673a\u9502\u8bd5\u5242 (1.2 eq.)\u52a0\u5165\u9002\u91cf\u6eb6\u5242\u7a00\u91ca (\u70f7\u57fa\u9502\u8bd5\u5242\uff0c\u91c7\u7528\u65e0\u6c34\u7532\u82ef\u7a00\u91ca\u81f3\u6d53\u5ea6\u4e3a0.36 M\uff1b\u70f7\u57fa\u9502\u8bd5\u5242\uff0c\u5219\u91c7\u7528\u65e0\u6c34THF\u7a00\u91ca\u81f3\u6d53\u5ea6\u4e3a0.6 M)\u3002\u968f\u540e\uff0c\u901a\u8fc7\u6ce8\u5c04\u6cf5\u7f13\u6162\u52a0\u5165 (\u8d85\u8fc71h\u540e\uff0c\u6ef4\u52a0\u5b8c\u6bd5)\u3002\u6ef4\u52a0\u7ed3\u675f\u540e\uff0c\u52a0\u5165\u9971\u548cNH_{4<\/sub>Cl\u6eb6\u6db2\u6dec\u706d\u53cd\u5e94\u3002\u6dec\u706d\u5b8c\u6210\u540e\uff0c\u5c06\u4e0a\u8ff0\u53cd\u5e94\u6db2\u52a0\u5165\u4e59\u919a\u8fdb\u884c\u8403\u53d6\uff0c\u5408\u5e76\u6709\u673a\u76f8\uff0c\u51cf\u538b\u9664\u53bb\u6eb6\u5242\u3002\u7c97\u4ea7\u7269\u91c7\u7528\u7845\u80f6\u67f1\u8272\u8c31 (\u6839\u636e\u4e0d\u540c\u4ea7\u7269\uff0c\u9009\u62e9\u6b63\u620a\u70f7\u6216\u6b63\u620a\u70f7\/\u4e59\u9178\u4e59\u916f100:3\u4f5c\u4e3a\u6d17\u8131\u5242)\u8fdb\u884c\u5206\u79bb\u7eaf\u5316\uff0c\u83b7\u5f97\u6700\u7ec8\u76ee\u6807\u4ea7\u7269\u3002<\/p>\n}}}}
\u53c2\u8003\u6587\u732e<\/strong><\/h4>\n\n
[1] M. Giannerini, M. Fa\u00f1an\u00e1s-Mastral, B. L. Feringa, Nat. Chem<\/em>. 2013<\/strong>, 5<\/em>, 667. doi: 10.1038\/nchem.1678<\/a>.<\/li>\n
[2] V. Hornillos, M. Giannerini, C. Vila, M. Fa\u00f1an\u00e1s-Mastral, B. L. Feringa, Org. Lett<\/em>. 2013<\/strong>, 15,<\/em> 5114. doi: 10.1021\/ol402408v<\/a>.<\/li>\n
[3] K. Fuji, S. Tamba, K. Shono, A. Sugie, A. Mori, J. Am. Chem. Soc<\/em>.\u00a02013<\/strong>, 135<\/em>, 12208. doi: 10.1021\/ja406374t<\/a>.<\/li>\n<\/ul>\n
\u672c\u6587\u7248\u6743\u5c5e\u4e8e\u00a0<\/strong>Chem-Station\u5316\u5b66\u7a7a\u95f4<\/strong><\/a>\uff0c \u6b22\u8fce\u70b9\u51fb\u6309\u94ae\u5206\u4eab\uff0c\u672a\u7ecf\u8bb8\u53ef\uff0c\u8c22\u7edd\u8f6c\u8f7d\uff01<\/strong><\/p>\n","protected":false},"excerpt":{"rendered":"\u6982\u8981 1975\u5e74\uff0c\u65e5\u672c\u5927\u962a\u5927\u5b66\u5e94\u7528\u5316\u5b66\u7cfb\u5de5\u5b66\u9662 (\u5927\u962a\u5927\u5b66\u5de5\u5b66\u90e8\u5fdc\u7528\u7cbe\u5bc6\u5316\u5b66\u79d1, Department of Applied Chemistry, Faculty of Engineering, Osaka University)\u7684\u6751\u6865\u4fca\u4e00 (\u6751\u6a4b \u4fca\u4e00, Murahashi Shun-ichi)\u7814\u7a76\u5ba4\u62a5\u9053\u4e86\u94af\u50ac\u5316\u5242\u91c7\u7528\u7684\u5364\u4ee3\u70ef\u70c3\u4e0e\u70f7\u57fa\u9502\u8bd5\u5242\u8fdb\u884c\u7684\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\uff0c\u7814\u7a76\u53d1\u73b0\u53cd\u5e94\u5177\u6709\u4f18\u826f\u7684\u7acb\u4f53\u9009\u62e9\u6027\uff0c\u5364\u4ee3\u70ef\u70c3\u6784\u578b\u5b8c\u5168\u4fdd\u6301[1]\u3002 1979\u5e74\uff0cMurahashi\u8fdb\u4e00\u6b65\u5c06\u9502\u8bd5\u5242\u6269\u5c55\u81f3\u82b3\u57fa\u4e0e\u6742\u82b3\u57fa\u9502\uff0c\u5e76\u5c06\u5e95\u7269\u6269\u5c55\u81f3\u4e0e\u82b3\u57fa\u5171\u8f6d\u7684\u5364\u4ee3\u70ef[2]\uff0c\u540c\u6837\u5177\u6709\u4f18\u826f\u7684\u7acb\u4f53\u9009\u62e9\u6027\u3002 1982\u5e74\uff0cG. Linstrumelle\u5c06\u8be5\u53cd\u5e94\u6761\u4ef6\u5e94\u7528\u4e8e\u8054\u70ef\u57fa\u9502\uff0c\u6210\u529f\u5b9e\u73b0\u8054\u70ef\u57fa\u9502\u7684\u4e59\u70ef\u57fa\u5316\u4e0e\u82b3\u57fa\u5316[3]-[4]\u3002 1987\u5e74\uff0cPelter\u6210\u529f\u5c06Murahashi\u7684\u53cd\u5e94\u6761\u4ef6\u6269\u5c55\u81f3\u82c4\u57fa\u4e0e\u8089\u6842\u57fa\u5364\u4ee3\u70f7[5]\uff0c\u5e76\u83b7\u5f97\u826f\u597d\u7684\u4ea7\u7387\u3002 \u867d\u7136\u4e0a\u8ff0\u53cd\u5e94\u6761\u4ef6\u5177\u6709\u5e7f\u6cdb\u7684\u5e95\u7269\u9002\u7528\u8303\u56f4\u4e0e\u8f83\u9ad8\u7684\u4ea7\u7387\u3002\u7136\u800c\uff0c\u90e8\u5206\u5e95\u7269\u5728\u8be5\u6761\u4ef6\u4e0b\u53cd\u5e94\u8f83\u6162\uff0c\u9700\u8981\u8f83\u9ad8\u7684\u6e29\u5ea6\u3001\u8fc7\u91cf\u7684\u6709\u673a\u9502\u8bd5\u5242\u53ca\u8f83\u957f\u7684\u53cd\u5e94\u65f6\u95f4\u3002\u540c\u65f6\uff0c\u7531\u4e8e\u9502\u8bd5\u5242\u8f83\u9ad8\u7684\u53cd\u5e94\u6d3b\u6027\uff0c\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u8fd8\u4f1a\u51fa\u73b0\u5364\u4ee3\u70c3\u4e4b\u95f4\u7684\u540c\u5076\u8054\u526f\u53cd\u5e94\u53ca\u9502-\u5364\u7d20\u4ea4\u6362\u8fc7\u7a0b\u5feb\u4e8e\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\u7684\u95ee\u9898\u3002\u56e0\u6b64\uff0c\u65e0\u6cd5\u9002\u5e94\u5927\u89c4\u6a21\u7684\u5b9e\u9a8c\u5ba4\u5408\u6210\u7814\u7a76\u53ca\u5de5\u4e1a\u751f\u4ea7\u30022010\u5e74\uff0cYoshida\u8bfe\u9898\u7ec4\u91c7\u7528\u6d41\u52a8\u578b\u5fae\u53cd\u5e94\u5668 (flow microreactor)\u5c06Li-Br\u4ea4\u6362\u4e0eMurahashi\u5076\u8054\u6210\u529f\u7ed3\u5408\uff0c\u987a\u5229\u5b8c\u6210\u4e86\u4e24\u79cd\u4e0d\u540c\u82b3\u5364\u95f4\u7684\u4ea4\u53c9\u5076\u8054\uff0c\u83b7\u5f97\u8f83\u9ad8\u7684\u4ea7\u7387\uff0c\u5e76\u4f7f\u53cd\u5e94\u65f6\u95f4\u6781\u5927\u7f29\u77ed[6]\u3002\u540c\u65f6\uff0c\u6709\u6548\u907f\u514d\u4e86\u540c\u79cd\u82b3\u5364\u95f4\u7684\u540c\u5076\u8054\u53cd\u5e94\u3002 2013\u5e74\uff0cFeringa\u91c7\u7528\u53cc(\u4e09\u53d4\u4e01\u57fa\u81a6)\u5408\u94af(II)\u6216Pd-PEPPSI-IPent\u3001Pd2(dba)3\/\u4e09\u53d4\u4e01\u57fa\u81a6\u53caPd2(dba)3\/XPhos\u50ac\u5316\u5242\uff0c\u6210\u529f\u5c06\u5e95\u7269\u8303\u56f4\u6269\u5c55\u81f3\u66f4\u591a\u7684\u82b3\u5364\u53ca\u7a20\u73af\u82b3\u5364\uff0c\u53cd\u5e94\u6761\u4ef6\u6e29\u548c\uff0c\u53cd\u5e94\u65f6\u95f4\u6709\u6548\u7f29\u77ed\uff0c\u540c\u6837\u907f\u514d\u4e86\u9502-\u5364\u7d20\u4ea4\u6362\u53ca\u540c\u5076\u8054\u7b49\u526f\u53cd\u5e94\u3002\u5177\u6709\u66f4\u4e3a\u5e7f\u6cdb\u7684\u5e95\u7269\u9002\u7528\u8303\u56f4\u53ca\u4f18\u826f\u7684\u53cd\u5e94\u9009\u62e9\u6027\u4e0e\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\uff0c\u751a\u81f3\u8fde\u63a5\u6709\u5bb9\u6613\u4e0e\u9502\u8bd5\u5242\u53d1\u751f\u4eb2\u6838\u53cd\u5e94\u7684\u916e\u7fb0\u57fa\u3001\u6c30\u57fa\u53ca\u70f7\u6c27\u7fb0\u57fa\u5b98\u80fd\u56e2\u76f8\u5173\u7684\u5e95\u7269\uff0c\u5747\u53ef\u5728\u8be5\u6761\u4ef6\u4e0b\u987a\u5229\u5b8c\u6210\u76f8\u5e94\u7684\u4ea4\u53c9\u5076\u8054[7]-[8]\u3002 \u4e4b\u540e\uff0cMori\u91c7\u7528Ni(II)-NHC\u50ac\u5316\u5242\uff0c\u5b9e\u73b0\u4e86Murahashi\u5076\u8054\u805a\u5408 (Murahashicoupling polymerization)\uff0c\u5c06\u8be5\u53cd\u5e94\u6210\u529f\u5e94\u7528\u4e8e\u03c0-\u5171\u8f6d\u805a\u5408\u7269 (\u03c0-conjugatedpolymers)\u7684\u5408\u6210[9]\u3002 2019\u5e74\uff0cFeringa\u4e0eOrgan\u5728\u6df1\u51b7\u6e29\u5ea6\u4e0b (cryogenic temperatures)\u4e0b\uff0c\u91c7\u7528\u53cd\u5e94\u6d3b\u6027\u66f4\u9ad8\u7684Pd-NHC\u50ac\u5316\u5242\uff0c\u901a\u8fc7\u6e29\u5ea6\u4f9d\u8d56\u7684\u5316\u5b66\u9009\u62e9\u6027\u5f15\u53d1\u7b56\u7565 (temperature-dependent chemoselectivity trigger)\uff0c\u6210\u529f\u5b9e\u73b0\u6c2f\u4ee3\u82b3\u57fa\u6eb4 (\u82b3\u57fa\u6c2f\u5728\u8be5\u6761\u4ef6\u4e0b\u65e0\u6cd5\u53c2\u4e0e\u5076\u8054\u8fc7\u7a0b)\u7684\u5316\u5b66\u9009\u62e9\u6027\u4ea4\u53c9\u5076\u8054[10]\u3002\u540c\u65f6\uff0c\u7814\u7a76\u53d1\u73b0\u542b\u6709\u82b3\u57fa\u6c2f\u5b98\u80fd\u56e2\u7684\u5076\u8054\u4ea7\u7269\u53ef\u4ee5\u5728\u4e00\u9505\u6761\u4ef6\u4e0b\u5b8c\u6210\u591a\u79cd\u540e\u7eed\u7684\u4e8c\u7ea7\u5076\u8054\u8fc7\u7a0b\uff0c\u5982Suzuki-Miyaura\u53cd\u5e94\u3001Negishi\u53cd\u5e94\u53caBuchwald-Hartwig\u53cd\u5e94\u7b49\u3002 \u6587\u732e\u4e2d\u5c06\u4e0a\u8ff0\u94af\u50ac\u5316\u7684\u5364\u4ee3\u70c3\u4e0e\u6709\u673a\u9502\u8bd5\u5242\u4e4b\u95f4\u7684\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\u79f0\u4e3aMurahashi\u5076\u8054\u53cd\u5e94 (Murahashi coupling)\u6216Murahashi\u4ea4\u53c9\u5076\u8054\u53cd\u5e94 (Murahashi cross-coupling)\u3002\u8be5\u53cd\u5e94\u5177\u6709\u5e7f\u6cdb\u7684\u5e95\u7269\u9002\u7528\u8303\u56f4\uff0c\u4f18\u826f\u7684\u5316\u5b66\u9009\u62e9\u6027\u4e0e\u7acb\u4f53\u9009\u62e9\u6027\u53ca\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u3002\u76ee\u524d\uff0cMurahashi\u5076\u8054\u53cd\u5e94\u5728\u6709\u673a\u5408\u6210\u65b9\u6cd5\u5b66\u7814\u7a76\u3001\u533b\u836f\u53ca\u6709\u673a\u6750\u6599\u7814\u7a76\u9886\u57df\u5177\u6709\u6781\u4e3a\u5e7f\u6cdb\u7684\u5e94\u7528\u524d\u666f\u3002 \u57fa\u672c\u6587\u732e [1] M. Yamamura, I. Moritani, S. Murahashi, J. Organomet. Chem. 1975, 91, C39. doi: 10.1016\/S0022-328X(00)89636-9. [2] S. Murahashi, M. Yamamura, K. Yanagisawa, N. Mita, K. Kondo, J. Org. Chem. 1979, 44, 2408. doi: 10.1021\/jo01328a016. [3] T. Jeffery-Luong, G. Linstrumelle, Synthesis 1982, 738. doi: 10.1055\/s-1982-29923. [4] S. Murahashi, J. Organomet. Chem. 2002, 653, 27. doi: 10.1016\/S0022-328X(02)01167-1. [5] A. Pelter, M. Rowlands, G. Clements, Synthesis 1987, 51. doi: 10.1055\/s-1987-27840. [6] A. 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\u53cd\u5e94\u673a\u7406<\/strong><\/h4>\n\u70ef\u57fa\u5364\u53c2\u4e0e\u7684<\/strong>Murahashi<\/strong>\u5076\u8054<\/strong><\/p>\n<\/a><\/p>\n\u82b3\u5364\u53c2\u4e0e\u7684<\/strong>Murahashi<\/strong>\u5076\u8054<\/strong><\/p>\n<\/a><\/p>\n

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\u82b3\u5364\u53c2\u4e0e\u7684<\/strong>Murahashi<\/strong>\u5076\u8054<\/strong><\/p>\n
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