General C(sp3)–C(sp3) Cross-Coupling of Primary Amines via in Situ Diazene Formation

Abstract

Primary amines are among the most abundant and readily available functional groups, yet their direct use as alkyl cross-coupling partners remains underdeveloped. We report a general platform for C(sp3)–C(sp3) cross-coupling enabled by the in situ formation and visible-light-induced denitrogenation of unsymmetric diazenes. Central to this approach is the development of N-benzoyloxysulfamides, which are readily prepared in a single step from primary amines and bench-stable O-benzoylhydroxylamines and undergo mild base-promoted conversion to diazenes. Subsequent photosensitized denitrogenation using an inexpensive organic triplet photosensitizer enables the direct union of two amine-derived fragments under operationally simple conditions. This telescoped, one-pot process avoids prefunctionalized organometallic reagents, tolerates a broad range of functional groups, and enables late-stage modification of complex molecules.