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This report details the development and implementation of a strategy to construct aryl- and heteroaryl sulfones via Ni/photoredox dual catalysis. Using aryl sulfinate salts, the C-S bond can be forged at room temperature under base-free conditions. An array of aryl- and heteroaryl halides are compatible with this approach. The broad tolerance and mild nature of the described reaction could potentially be employed to prepare sulfones with biological relevance ( e.g. , in bioconjugation, drug substance synthesis, etc. ) as demonstrated in the synthesis of drug-like compounds or their precursors. When paired with existing Ni/photoredox chemistry for C sp 3  -C sp 2  cross-coupling, an array of diverse sulfone scaffolds can be readily assembled from bifunctional electrophiles. A mechanistic manifold consistent with experimental and computational data is presented.

Engaging sulfinate salts via Ni/photoredox dual catalysis enables facile Csp2–SO2R coupling

Engaging sulfinate salts via Ni/photoredox dual catalysis enables facile C_sp2–SO₂R coupling