Chiral Phosphine−Olefin Ligands in the Rhodium-Catalyzed Asymmetric 1,4-Addition Reactions
Authors:
- 24 January 2007
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 129 (7) , 2130-2138
Abstract
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.Keywords
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