Far from being a well-understood reaction, the enantioselective hydrogenation of prochiral olefins with Rh–and Ru–bisphosphane catalysts (see picture, M=Rh, Ru) has recently shown some surprises. Among them are a catalytic cycle featuring initial addition of hydrogen to the catalyst and not the catalyst–substrate complex as well as a purely ionic mechanism.
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Kai Rossen (2001) studied this question.
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