Catalytic Cycle of Rhodium-Catalyzed Asymmetric 1,4-Addition of Organoboronic Acids. Arylrhodium, Oxa-π-allylrhodium, and Hydroxorhodium Intermediates
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- 11 April 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (18) , 5052-5058
- https://doi.org/10.1021/ja012711i
Abstract
The catalytic cycle of asymmetric 1,4-addition of phenylboronic acid to an α,β-unsaturated ketone catalyzed by a rhodium−binap complex was established by use of RhPh(PPh3)(binap) as a key intermediate. The reaction proceeds through three intermediates, phenylrhodium, oxa-π-allylrhodium, and hydroxorhodium complexes, all of which were observed in NMR spectroscopic studies. The transformations between the three intermediates, that is, insertion, hydrolysis, and transmetalation, were also observed. On the basis of the catalytic cycle, a more active chiral catalyst, [Rh(OH)(binap)]2, was found and used successfully for the asymmetric 1,4-addition reactions.Keywords
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