Singlet Carbenes Are Stereoinductive Main Group Ambiphiles

Stereogenic units are a critical source of molecular complexity, but their stereoselective formation via main group ambiphiles─which are suitable for derivatizing a wide scope of functionalities─is largely unexplored. Herein, using chiral cyclic (alkyl)(amino)carbenes (^ChiCAACs), we study stereoinduction during the oxidative addition of E–H σ-bonds (E = C, N, O, Si, P). Through computational modeling, the relationship between stereochemical outcome and mechanism is elucidated, providing insight into when and why ^ChiCAACs exhibit excellent stereoselectivities. Altogether, these results demonstrate the potential for chiral main group ambiphiles to generate stereogenic units in a highly controlled manner opening avenues for applying “metal-like” reactivity in metal-free asymmetric syntheses.