Direct Stereoconvergent Allylation of Chiral Alkylcopper Nucleophiles with Racemic Allylic Phosphates

Copper‐catalyzed stereoconvergent allylation of chiral sp 3 ‐hybridized carbon nucleophiles with a racemic mixture of acyclic secondary allylic phosphates is reported. In the presence of a copper‐catalyst complexed with chiral BenzP* ligand, tandem coupling reaction of vinyl arenes, bis(pinacolato)diboron, and racemic allylic phosphates provided β‐chiral alkylboronates possessing ( E )‐alkenyl moiety through a direct stereoconvergent allylic coupling with concomitant generation of a C(sp 3 )‐stereogenic center. A range of vinyl (hetero)arenes and secondary allylic phosphates bearing 1°, 2°, 3° alkyl and phenyl α‐substituents were suitable for the reaction, forming products with high enantioselectivities up to 95 % ee . Density functional theory calculations were conducted in detail to elucidate the origin of the observed regioselectivity of borylcupration and stereoconvergent ( E )‐olefin formation from racemic allylic phosphates.