Dehydrogenation of secondary amines to imines catalyzed by an iridium PCP pincer complex: initial aliphatic or direct amino dehydrogenation?
Dehydrogenation of secondary amines to imines catalyzed by an iridium PCP pincer complex: initial aliphatic or direct amino dehydrogenation?
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DOI：
10.1016/s1381-1169(02)00200-5
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发表时间：
2002-10-16
影响因子：
--
通讯作者：
Jensen, CM
中科院分区：
文献类型：
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作者：
Gu, XQ;Chen, W;Jensen, CM
PCP 钳配合物 IrH2(C6H3-2,6-(CH(2)PBut(2))(2)) 催化仲胺向亚胺的转移脱氢。该催化体系对空间和电子因素高度敏感，在不对称底物环己乙胺和苄基丙胺的脱氢反应中观察到大于 99% 的区域选择性。当反应在甲苯溶液中进行时，可获得良好至优异的产率。 2,2,2',2'-四甲基二丁胺的脱氢仅导致相应亚胺的产生，表明催化反应途径涉及直接的氨基而不是最初的脂肪族脱氢。 (C) 2002 Elsevier Science B.V. 保留所有权利。
The PCP pincer complex, IrH2(C6H3-2,6-(CH(2)PBut(2))(2)) catalyzes the transfer dehydrogenation of secondary amines to imines. The catalytic system is highly sensitive to both steric and electronic factors and greater than 99% regioselectivity are observed in the dehydrogenation of the asymmetric substrates, cyclohexyethylamine and benzylpropyl amine. Good to excellent yields are obtained when the reactions are carried out in toluene solution. The dehydrogenation of 2,2,2',2'-tetramethyldibutylamine leads exclusively to the production of the corresponding imine indicating that the catalytic reaction pathway involves direct amino rather than initial aliphatic dehydrogenation. (C) 2002 Elsevier Science B.V. All rights reserved.