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.
Keywords: P-benzylation; P-stereogenic phosphines; kinetic resolution; palladium/Xiao-Phos; sec-phosphine Oxides.
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