Synergistic Merger of Ketone, Halogen Atom Transfer (XAT), and Nickel-Mediated C(sp3)-C(sp2) Cross-Electrophile Coupling Enabled by Light.

Abstract

In the present manuscript, we have developed a unique catalytic system by merging photoexcited ketone catalysis, halogen atom transfer (XAT), and nickel catalysis to forge C(sp3)-C(sp2) cross-electrophile coupling products from unactivated iodoalkanes and (hetero)aryl bromides. The synergistic catalytic system works under mild reaction conditions and tolerates a variety of functional groups; moreover, this strategy allows the late-stage modification of medicinally relevant molecules. Preliminary mechanistic studies reveal the role of the α-aminoalkyl radical, which further participates in the XAT process with alkyl iodides to generate the desired alkyl radical, which eventually intercepts with the nickel catalytic cycle to liberate the products in good to excellent yields.