A remarkable anion effect on the enantioselectivity of the Pd-catalyzed allylic amination using ferrocenyl ligands

被引：117

作者：

Burckhardt, U ^{[1
]}

Baumann, M ^{[1
]}

Togni, A ^{[1
]}

机构：

[1] SWISS FED INST TECHNOL,ETH ZENTRUM,INORGAN CHEM LAB,CH-8092 ZURICH,SWITZERLAND

来源：

TETRAHEDRON-ASYMMETRY | 1997年 / 8卷 / 01期

关键词：

D O I：

10.1016/S0957-4166(96)00486-7

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The effect of several anions on the enantioselectivity of the Pd-catalyzed substitution reaction of 1,3-diphenylprop-2-enylethyl carbonate 1 with benzylamine, utilizing chiral ferrocenyl ligands such as 1-{(R)-1-[(S)-2-(diphenylphosphino)-ferrocenyl]ethyl}- 3-(1-adamantyl)-1H-pyrazole 3a, was investigated. Small hard anions such as F- and BH4-, added in co-catalytic amounts to the catalyst, were found to enhance the ee to >99.5%. On the other hand, non-coordinating anions, e.g. PF6-, had a detrimental effect on the enantioselectivity (<10% ee). The beneficial effect of fluoride is discussed in terms of its establishing Curtin-Hammett conditions, by virtue of its coordination to Pd. (C) 1997, Elsevier Science Ltd. All rights reserved.

引用

页码：155 / 159

页数：5

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