Ring-Opening Decarbonylative C(sp³)–C(sp³) Cross-Electrophile Coupling of Cyclic Imides with Unactivated Alkyl Chlorides

We report a nickel-mediated decarbonylative cross-electrophile coupling of N-Boc succinimides and glutarimides with unactivated alkyl chlorides. The transformation proceeds via selective endocyclic N–C(O) activation, which opens a new entry point into C(sp³)–C(sp³) cross-electrophile coupling and, through incorporation of the ring-opened imide scaffold, establishes a highly modular platform to rapidly build molecular complexity. In situ halide exchange enables the use of abundant alkyl chlorides, while broad functional group tolerance grants access to structurally diverse α- and β-substituted amides. As a re-sult, the method provides a new retrosynthetic disconnection to aliphatic amides, exemplified by the synthesis of densely substituted carbocycles and novel capsaicin derivatives.