Transition metal-catalyzed enantioselective C–P coupling reactions for the construction of P-stereogenic centers

The transition metal-catalyzed C–P coupling reaction represents an effective strategy for the construction of P-stereogenic centers. These reactions involve different stereochemical mechanistic details depending on the phosphorus starting materials employed. The stereospecific transition metal-catalyzed C–P coupling of enantioenriched P-stereogenic compounds was mainly investigated in the early days. With the development of asymmetric catalysis, corresponding efficient kinetic resolution and dynamic kinetic asymmetric C–P coupling of racemic P-stereogenic starting compounds have recently been disclosed. This perspective discusses the impressive advances and provides an outlook on the directions of further developments. Challenges and opportunities: • The replacement of precious metals (platinum, palladium, ruthenium, etc.) with earth-abundant first-row transition metals, such as copper, nickel, and cobalt, as catalysts for developing enantioselective C–P coupling is an appealing future direction. • Extraordinary efforts are still required to expand the scopes of both phosphorus starting materials as well as electrophiles. • Enantioselective C–P cross-coupling reactions that embody dynamic kinetic resolution or DyKAT of racemic phosphorus starting materials are greatly appealing in terms of both reaction efficiency and practicality. Transition metal-catalyzed enantioselective C–P coupling reaction represents a powerful method for the construction of P-stereogenic centers. This strategy involves different stereochemical mechanistic details depending on the phosphorus starting materials employed. This perspective by Gu, Liu, and colleagues summarizes the impressive advances and provides an outlook on the directions of further developments.