Synthesis of α‐Aminophosphines by Copper‐Catalyzed Regioselective Hydroamination of Vinylphosphines.

Abstract: A copper‐catalyzed net hydroamination of vinylphosphine boranes with hydrosilanes and O‐benzoylhydroxylamines has been developed. The reaction proceeds regioselectively to form the corresponding α‐aminophosphine boranes of potent interest in medicinal and pharmaceutical chemistry. This copper catalysis is based on an umpolung, electrophilic amination strategy and provides a new electrophilic amination approach to α‐aminophosphine derivatives. Additionally, although still preliminary, asymmetric synthesis has also been achieved by judicious choice of a chiral bisphosphine‐ligated copper complex. [ABSTRACT FROM AUTHOR]