“…To this end, transition metal (TM)-catalyzed asymmetric C(cp 3 )–C(sp 3 ) coupling and asymmetric hydrogenation of olefins represent general and widely used techniques for accessing contiguous stereogenic centers. − Nevertheless, the one-step catalytic construction of vicinal stereocenters with full control of the stereoselectivity remains a synthetic challenge. Since the seminal work by Carreira et al in 2013, stereodivergent dual catalysis has emerged as an effective route to stereochemically complex molecules with full control of enantio- and diastereoselectivity. − The strategy typically utilizes the coupling between a chiral transition metal–allyl electrophile and a chiral organic or organometallic nucleophile to construct C(sp 3 )–C(sp 3 ) bonds bearing two vicinal stereocenters. − ,− In the past decade, numerous research groups, including those of Zhang, − Wang, − Hartwig, , Zi, He, Kitamura, Guo, and Feng have made significant contributions to the progress of stereodivergent dual bimetallic catalysis in asymmetric allylic substitution, providing rapid access to multichiral molecules from identical initial materials . Compared to the experimental advancements, computational studies on stereodivergent dual TM catalysis remain limited, − ,− largely due to the complexity of these multicomponent systems and the large-scale structures involved (at the level of 200–250 atoms).…”