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

Qiang Dai; Lu Liu; Junliang Zhang

doi:10.1002/anie.202111957

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

Angew Chem Int Ed Engl. 2021 Dec 20;60(52):27247-27252. doi: 10.1002/anie.202111957. Epub 2021 Nov 16.

Authors

Qiang Dai¹, Lu Liu¹, Junliang Zhang^{2

3}

Affiliations

¹ School of Chemistry and Molecular Engineering and Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, East China Normal University, Shanghai, 200241, P. R. China.
² Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai, 200438, P. R. China.
³ School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan, 453007, P. R. China.

PMID: 34672416
DOI: 10.1002/anie.202111957

Abstract

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.

Publication types

Research Support, Non-U.S. Gov't

Abstract

Publication types

Grants and funding