Construction of P‐Chiral Alkenylphosphine Oxides through Highly Chemo‐, Regio‐, and Enantioselective Hydrophosphinylation of Alkynes

Abstract Alkenylphosphine oxides have a wide spectrum of practical applications. However, chemo‐, regio‐, and enantiocontrolled construction of this structural motif still constitutes a significant synthetic challenge. Here we show that these compounds can be efficiently accessed by using a palladium/Xiao‐Phos catalytic system, which leads to the highly regioselective formation of the anti‐Markovnikov adducts through addition of a secondary phosphine oxide to an alkyne. Diverse (hetero)aryl and alkyl alkynes, as well as both terminal and internal alkynes can be employed as substrates. The kinetic resolution process makes it possible to produce alkenylphosphine oxide and recovered secondary phosphine oxides with high ee values. Further transformations of these two P‐chiral scaffolds confirm the high practicability and application prospect of our synthetic strategies. Initial mechanistic studies strongly suggested that hydropalladation is likely responsible for the conversion process.