Palladium/Xiao-Phos-Catalyzed Kinetic Resolution of sec-Phosphine Oxides by P-Benzylation

P-stereogenic tert- and sec-phosphines have wide applications in asymmetric catalysis, materials, and pharmaceutical chemistry, however, their practical synthesis still constitutes a significant challenge. Herein, a successful kinetic resolution of rac-secondary phosphine oxides via the enantioselective P-benzylation process catalyzed by the palladium/Xiao-Phos was designed. Both tert- and sec-phosphine oxides were delivered in good yield and excellent enantiopurity (selectivity factor up to 226.1). The appealing synthetic utilities are further demonstrated by the facile preparation of several valuable P-chiral compounds, precursors of bidentate ligands, as well as transition metal complexes.

Automated summary

This study successfully achieved the kinetic resolution of rac-secondary phosphine oxides via enantioselective P-benzylation catalysis, delivering both tert- and sec-phosphine oxides in good yield and excellent enantiopurity. The synthetic utilities were further demonstrated by the facile preparation of valuable P-chiral compounds, precursors of bidentate ligands, and transition metal complexes.