Chiral Phosphine−Olefin Ligands in the Rhodium-Catalyzed Asymmetric 1,4-Addition Reactions

A full overview on the use of chiral phosphine−olefin ligands 1 in the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds is described. Effective chiral environment of a Rh/1 complex was shown to resemble that of a Rh/(R,R)-Ph-bod* complex by compari...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2007-02, Vol.129 (7), p.2130-2138
Main Authors: Duan, Wei-Liang, Iwamura, Hiroshi, Shintani, Ryo, Hayashi, Tamio
Format: Article
Language:English
Subjects:
Alkenes - chemical synthesis
Alkenes - chemistry
Boronic Acids - chemistry
Bridged Bicyclo Compounds - chemical synthesis
Bridged Bicyclo Compounds - chemistry
Catalysis
Crystallography, X-Ray
Kinetics
Ligands
Molecular Structure
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Phosphines - chemical synthesis
Phosphines - chemistry
Rhodium - chemistry
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Summary:A full overview on the use of chiral phosphine−olefin ligands 1 in the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds is described. Effective chiral environment of a Rh/1 complex was shown to resemble that of a Rh/(R,R)-Ph-bod* complex by comparing the experimental results as well as the X-ray crystal structures. High catalytic activity of a Rh/1 complex was disclosed and the catalytic cycle involving a trimer−monomer equilibrium was established through mechanistic studies using a reaction calorimeter and 31P NMR spectroscopy. A negative nonlinear effect derived from an inactive trimer−active monomer equilibrium of the catalyst was also successfully observed.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja0671013