A Bifunctional Sulfone Reagent for Asymmetric Aminomethylative Sulfonylation of Dienes

Sulfone reagents have emerged as highly versatile coupling partners in transition-metal catalysis, owing to their exceptional reactive flexibility. However, current C-SO₂ activation strategies in sulfone reagents remain constrained to introducing single- or double-electron acceptors onto the departing sulfonyl moieties, which inadvertently diminishes the reactivity of the resulting sulfinate and prevents its reutilization. To tackle the long-standing dichotomy between C-SO₂ bond cleavage and reconstruction, we report a neighboring nitrogen-directed C-SO₂ activation strategy, thereby inventing a novel aminomethyl sulfone reagent. The application of this aminomethyl sulfone reagent was showcased by the palladium-catalyzed asymmetric aminomethylative sulfonylation of dienes to forge a variety of chiral 1,3-amino sulfones. The extensive substrate compatibility, unparalleled reactivity, and unprecedented high stereoselectivity demonstrated the great potential of this reagent in synthetic chemistry.