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A range or electron-poor and heterocyclic sulfonamides react with phenylacetyl chlorides to produce benzhydryl derivatives in a single step. The reaction proceeds via tandem amide bond formation -Dohmori-Smiles rearrangement under simple conditions of aqueous base. In the case of o-nosylamides further reaction takes place at the nitro group to yield indazoles. Aryl and heteroaryl structures are fundamental to natural products and man-made molecules, and are frequently synthesized using stoichiometric organometallics and precious transition metal catalysts. These methods, while effective and hugely influential, are costly and environmentally unsustainable, making metal-free arylation methods 1 a key objective for future strategies in synthetic chemistry. We are interested in harnessing simple aryl sulfonamides as metal-free arylating agents in this regard, through the process set out in Scheme 1. The nitrogen atom acts as a nucleophilic trap for an electrophilic coupling partner, a benzyne in this example, generating an incipient carbanion (3) that triggers a 1,5-desulfonylative Smiles rearrangement. 2,3,4 Overall, the process repositions a cheap and readily available building block as both an arylating and aminating agent, critical transformations in the pharmaceutical industry, whilst proceeding without recourse to metal reagents.

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