Part III. COD versus NBD precatalysts. Dramatic difference in the asymmetric hydrogenation of prochiral olefins with five-membered diphosphine Rh-hydrogenation catalysts

被引：67

作者：

Drexler, HJ ^{[1
]}

Baumann, W ^{[1
]}

Spannenberg, A ^{[1
]}

Fischer, C ^{[1
]}

Heller, D ^{[1
]}

机构：

[1] Univ Rostock, Inst Organ Katalyseforsch, D-18055 Rostock, Germany

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2001年 / 621卷 / 1-2期

关键词：

D O I：

10.1016/S0022-328X(00)00756-7

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Induction periods in the asymmetric hydrogenation of prochiral olefins with five-membered chelates of the type [Rh(PP)(diolefin)]BF4 originate from the parallel-running hydrogenation of the prochiral substrate and the diolefin that enters the system as a constituent of the precatalyst. Reactivities towards the most commonly used diolefins COD or NBD can differ by three powers of ten. X-ray crystal structure analyses of [Rh((S,S)-Et-DuPHOS)(NBD)]BF4 and of [Rh((R,R)-Et-DuPHOS)(COD)]BF4 imply that a recently discussed relation between the sense of rotation of the diolefin in the precatalyst (clockwise or anticlockwise twist) is not very likely. (C) 2001 Elsevier Science B.V. All rights reserved.

引用

页码：89 / 102

页数：14

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