Regiodivergent Sulfonylarylations of 1,3-Enynes via Nickel/Photoredox Dual Catalysis

Catalytic difunctionalization of 1,3-enynes represents an efficient and versatile approach to rapidly assemble multifunctional propargylic compounds, allenes and 1,3-dienes. Controlling selectivity in such addition reactions has been a long-standing challenging task due to multiple reactive centers resulted from conjugated structure of 1,3-enynes. Herein, we present a straightforward method for regiodivergent sulfonylarylations of 1,3-enynes via dual nickel and photoredox catalysis. Hinging on the nature of the 1,3-enynes, diverse reaction pathways are feasible; synthesis of α-allenyl sulfones via 1,4-sulfonylarylation, or preparation of (E)-1,3-dienyl sulfones with high chemo-, regio- and stereoselectivity through 3,4-sulfonylarylation. Notably, this is the first example that nickel and photoredox catalysis are merged to achieve efficient and versatile difunctionalizations of 1,3-enynes.