Abstract
The development and mechanism of the highly chemo- and enantioselective organocatalytic hydrophosphination reaction of alpha,beta-unsaturated aldehydes is presented. The reactions are catalyzed by protected chiral diarylprolinol derivatives and give access to optically active phosphine derivatives in high yields with up to 99% ee. The organocatalytic addition of other phosphorus nucleophiles was also investigated. The origin of the high enantioselectivity for the reaction with diphenylphosphine as the nucleophile is investigated by density functional theory calculations.