Asymmetric Conjugate 1,4-Addition of Arylboronic Acids to α,β-Unsaturated Esters Catalyzed by Rhodium(I)/(S)-binap
- 23 August 2000
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 65 (19), 5951-5955
- https://doi.org/10.1021/jo0002184
Abstract
Arylboronic acids underwent the conjugate 1,4-addition to α,β-unsaturated esters to give β-aryl esters in high yields in the presence of a rhodium(I) catalyst. The addition of arylboronic acids to isopropyl crotonate resulted in high yields and high enantioselectivity exceeding 90% ee in the presence of 3 mol % of Rh(acac)(C2H4)2 and (S)-binap at 100 °C. The rhodium/(S)-binap complex provided (R)-3-phenylbutanoate in the addition of phenylboronic acid to benzyl crotonate. The effects on the enantioselectivity of chiral phosphine ligands, rhodium precursors, and substituents on α,β-unsaturated esters are discussed, as well as the mechanistic aspect of the catalytic cycle.Keywords
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