THE IMPORTANCE OF PHOSPHINE-TO-RHODIUM RATIOS IN ENANTIOSELECTIVE HYDROBORATIONS
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abstract
Catalyzed hydroborations of several 1,1-disubstituted aryl alkenes were studied. Formation of tertiary alcohols (after oxidation) was favored when high phosphine-to-rhodium ratios were used. Enantioselective variants of this process can give chiral primary and tertiary alcohols with different enantioselectivities indicative of mechanistic differences. Measurements of product optical yields as a function of optical purities of the catalyst gave a linear correlation. The mechanistic implications of these data are discussed. 1994.