We developed a new family of chloride-bridged dinuclear rhodium(III) complexes bearing chiral diphosphien ligands, which were synthesized from a rhodium(I) precursor, [RhCl(cod)]2, chiral diphosphine ligands, and HCl. Complexes 1 acted as efficient catalysts for asymmetric hydrogenation of (E)-prop-1-ene-1,2-diyldibenzene and its derivatives without any directing groups. Notably, widely-used rhodium(I) catalytic systems required a directing group for high enantioselectivity. In addition, the present catalytic system based on rhodium(III) was applied to asymmetric hydrogenation of allylic alcohols, alkenylboranes, and unsaturated cyclic sulfones.

Chiral dinuclear rhodium(III) complexes as catalyst precursors for asymmetric hydrogenation of simple olefins

253rd National Meeting (2017)

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