The strong influence of various anions upon the hydrogenation of 2-phenyl-1-butene, catalyzed by chiral rhodium catalysts was investigated. Both sulfonates and halides exert large increases in the enantioselectivity when [Rh{(−)-bdpp}(NBD)]ClO4 (bdpp=2,4-bis(diphenylphosphino)pentane, NBD=2,5-norbornadiene) is used as the catalyst precursor at high pressures (70 atm) of dihydrogen in nonpolar solvents. A dihydride mechanism similar to that for Wilkinson\u27s catalyst [RhCl(PPh3)3] was shown to be operating at both high- and low-pressure conditions through a combination of catalytic studies, 31P, 1H and parahydrogen-induced polarization (PHIP) NMR experiments. With sulfonate and in neat methanol, however, a mechanistic switch takes place from a dihydride route (dihydrogen addition before olefin binding) at high pressure to an unsaturate route (olefin binding before dihydrogen addition) at low pressures (\u3c30 \u3eatm). Olefin isomerization is inhibited by halide addition, but occurs with sulfonate and in neat methanol through what is most likely a π-allyl mechanism. A detailed understanding of the effects of addition of these anions is crucial for development of new classes of catalysts capable of efficient enantioselective reduction of prochiral olefins lacking a secondary polar binding group
