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钌催化芳胺与乙烯和1,3 - 二烯的分子间偶联反应：关于氢胺化与邻位C-H键活化的机理洞察

Ruthenium-catalyzed intermolecular coupling reactions of arylamines with ethylene and 1,3-dienes: mechanistic insight on hydroamination vs ortho-C-H bond activation.

作者信息

Yi Chae S, Yun Sang Young

机构信息

Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201-1881, USA.

出版信息

Org Lett. 2005 May 26;7(11):2181-3. doi: 10.1021/ol050524+.

DOI:10.1021/ol050524+
PMID:15901164
Abstract

[reaction: see text]. The cationic ruthenium complex [(PCy3)2(CO)(Cl)Ru=CHCH=C(CH3)2]+BF4- was found to be an effective catalyst for the coupling reaction of aniline and ethylene to form a approximately 1:1 ratio of N-ethylaniline and 2-methylquinoline products. The analogous reaction with 1,3-dienes resulted in the preferential formation of Markovnikov addition products. The normal isotope effect of k(NH)/k(ND) = 2.2 (aniline and aniline-d7 at 80 degrees C) and the Hammett rho = -0.43 (correlation of para-substituted p-X-C6H4NH2) suggest an N-H bond activation rate-limiting step for the catalytic reaction.

摘要

[反应：见正文]。发现阳离子钌配合物[(PCy3)2(CO)(Cl)Ru=CHCH=C(CH3)2]+BF4-是苯胺与乙烯偶联反应生成N-乙基苯胺和2-甲基喹啉产物比例约为1:1的有效催化剂。与1,3-二烯的类似反应导致马尔科夫尼科夫加成产物的优先形成。k(NH)/k(ND)=2.2（80℃下苯胺和苯胺-d7）的正常同位素效应以及哈米特ρ=-0.43（对位取代的p-X-C6H4NH2的相关性）表明催化反应的限速步骤为N-H键活化。

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