Rhodium-Catalyzed 1,4-Addition of Arylboronic Acids to α,β-Unsaturated Carbonyl Compounds: Large Accelerating Effects of Bases and Ligands
- 1 July 2003
- journal article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 68 (15) , 6000-6004
- https://doi.org/10.1021/jo0207067
Abstract
The effects of ligands and bases in the rhodium(I)-catalyzed 1,4-addition of arylboronic acids to alpha,beta-unsaturated carbonyl compounds were reinvestigated to carry out the reaction under mild conditions. Rhodium(I) complexes possessing a 1,5-cyclooctadiene (cod) and a hydroxo ligand such as [RhOH(cod)](2) exhibited excellent catalyst activities compared to those of the corresponding rhodium-acac or -chloro complexes and their phosphine derivatives. The reaction was further accelerated in the presence of KOH, thus allowing the 1,4-addition even at 0 degrees C. A cationic rhodium(I)-(R)-binap complex, [Rh(R-binap)(nbd)]BF(4), catalyzed the reaction at 25-50 degrees C in the presence of Et(3)N with high enantioselectivities of up to 99% ee for alpha,beta-unsaturated ketones, 92% for aldehydes, 94% for esters, and 92% for amides.Keywords
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