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

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. [ABSTRACT FROM AUTHOR]