Diastereo‐ and Enantioselective Hydrophosphination of Cyclopropenes under Lanthanocene Catalysis.

The asymmetric hydrophosphination of cyclopropenes with phosphines is of much interest and importance, but has remained hardly explored to date probably because of the lack of suitable catalysts. We report here the diastereo‐ and enantioselective hydrophosphination of 3,3‐disubstituted cyclopropenes with phosphines by a chiral lanthanocene catalyst bearing the C2‐symmetric 5,6‐dioxy‐4,7‐trans‐dialkyl‐substituted tetrahydroindenyl ligands. This protocol offers a selective and efficient route for the synthesis of a new family of chiral phosphinocyclopropane derivatives, featuring 100 % atom efficiency, good diastereo‐ and enantioselectivity, broad substrate scope, and no need for a directing group. [ABSTRACT FROM AUTHOR]