Manganese-Catalyzed Synthesis of γ-Hydroxy Phosphine Oxides by Addition of Phosphine Oxides to Allylic Alcohols.

A manganese(II)-catalyzed anti-Markovnikov addition of diarylphosphine oxides to primary and secondary allylic alcohols has been developed, which delivered synthetically valuable γ-hydroxy phosphine oxides. The reaction proceeds under mild, base-assisted conditions with a broad substrate scope and excellent functional group tolerance. Mechanistic studies indicate the involvement of a homogeneous catalytic system and a radical pathway. The reaction is devoid of side products, retains the hydroxy motif, and enables late-stage derivatization, offering an atom-economical approach to organophosphorus compounds.