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The synthesis of P -stereogenic building blocks is extremely difficult. Herein we report an efficient kinetic resolution of secondary phosphine oxides via a Le-Phos-catalyzed asymmetric allylation reaction with Morita-Baylis-Hillman carbonates. This method provides facile access to enantioenriched secondary and tertiary P -chiral phosphine oxides with broad substrate scope, both of which could serve as P -stereogenic synthons, and can be rapidly incorporated into a given scaffold bearing a P -stereocenter. The highly desirable late stage modifications demonstrate the practicability of our method and can be a critical contribution to obtaining optimal P -chiral catalysts and ligands.

Access to P-chiral sec- and tert-phosphine oxides enabled by Le-Phos-catalyzed asymmetric kinetic resolution