•Olefin synthesis by para-nitro sulfonylhydrazone and sulfinates under aerobic condition.•Reaction proceeds via Pd-carbene intermediate migratory insertion.•Methodology obviates preparation of organometallic coupling partner and vinyl cation synthon.This Letter describes the synthesis of olefins by coupling of electron deficient sulfonylhydrazones with aryl sulfinate salts in the presence of a palladium(II) catalyst under aerobic conditions. This methodology obviates the need for preparation of an organometallic and separate activation of the ketone starting material via a vinyl halide or triflate. The oxidant, reagent stoichiometry, and the electronics of the sulfinate coupling partner are reported.

A novel reactivity of sulfonylhydrazones under Pd catalysis is described, where SO2 and N2 are formally extruded to afford the product of an apparent internal coupling reaction. The reaction is effective with both carbocyclic and heterocyclic aromatic precursors.

This paper describes a new reactivity of the Pd-catalyzed coupling of 2-amino-3-bromo-aromatic and heteroaromatic compounds with sulfonylhydrazones (Barluenga reaction).The new catalyst system and modulation of the electronic nature of hydrazone that were needed for successful reaction are described herein.