Carbene-Catalyzed Enantioselective Hydrophosphination of α-Bromoenals to Prepare Phosphine-Containing Chiral Molecules

Disclosed herein is the first carbene-organocatalyzed asymmetric addition of phosphine nucleophiles to the in situ generated alpha,beta-unsaturated acyl azolium intermediates. Our reaction enantioselectively constructs carbon-phosphine bonds and prepares chiral phosphines with high optical purities. The phosphine products are suitable for transforming to chiral ligands or catalysts with applications in asymmetric catalysis. The diarylalkyl or trialkyl phosphine products from our catalytic reactions, air-sensitive and reactive in nature, can be trapped (and stored) in their sulfur-oxidized form for operational simplicities.

Automated summary

This study presents a novel carbene-catalyzed reaction for the efficient synthesis of chiral phosphines. These phosphines can serve as chiral ligands or catalysts with broad applications in asymmetric catalysis.