Asymmetric Catalytic 1,2‐Dihydrophosphination of Secondary 1,2‐Diphosphines – Direct Access to Free P*‐ and P*,C*‐Diphosphines

Abstract A 1,2‐dihydrophosphination of bis(phenylphosphino)ethane with a wide range of activated olefins was achieved in a catalytic manner with enantiomeric and diastereomeric excess of up to >99% and 44% respectively. The protocol can be extended to selected substrates leading to free P ‐ and C ‐chiral 1,2‐diphosphines. The synthesized ligands can also undergo direct complexation onto palladium affording complexes with complete retention of stereo‐integrity. magnified image