Catalytic Cycle of Rhodium-Catalyzed Asymmetric 1,4-Addition of Organoboronic Acids. Arylrhodium, Oxa-π-allylrhodium, and Hydroxorhodium Intermediates

2002/04/11 by Tamio Hayashi, Makoto Takahashi, Yoshiaki Takaya +1 · 2 citations
Chemistry · #Asymmetric Hydrogenation and Catalysis #Catalytic Cross-Coupling Reactions #Cyclopropane Reaction Mechanisms

paper · doi:10.1021/ja012711i

openalex publication_date 2002/04/11 · openalex created_date 2016/06/24 · openalex updated_date 2026/06/24

Abstract

The catalytic cycle of asymmetric 1,4-addition of phenylboronic acid to an alpha,beta-unsaturated ketone catalyzed by a rhodium-binap complex was established by use of RhPh(PPh(3))(binap) as a key intermediate. The reaction proceeds through three intermediates, phenylrhodium, oxa-pi-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.

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