Generation of Stereocenters via Single-Carbon-Atom Doping Using <i>N</i> -Isocyanides

Atomic carbon remains a challenging species for organic synthesis despite its potential to form four covalent bonds in a single step. Single-carbon-atom doping (SCAD) offers a powerful approach to enhancing molecular complexity in one process without atom loss. However, synthetically viable SCAD reactions capable of generating stereocenters have not been realized. Here, we report an SCAD reaction that creates stereocenters by unlocking the reactivity of (<i>N</i>-isocyanoimino)phosphorane as an atomic carbon equivalent. This reagent facilitates the single-step conversion of various acyl chlorides into homologated α-chloro cyclic ketones, proceeding via the formation of four different bonds: one C-Cl, one C-H, and two C-C bonds at the incorporated carbon atom.