O-Benzyl Xanthate Esters under Ni/Photoredox Dual Catalysis: Selective Radical Generation and Csp3–Csp2 Cross-Coupling

Alkyl xanthate esters are perhaps best known for their use in deoxygenation chemistry. However, their use in cross-coupling chemistry has not been productive, which is due, in part, to inadequate xanthate activation strategies. Herein, we report the use of O -benzyl xanthate esters, readily derived from alcohols, as radical pronucleophiles in Csp 3 -Csp 2 cross-couplings under Ni/photoredox dual catalysis. Xanthate (C-O) cleavage is found to be reliant on photogenerated ( sec -butyl) radical activators to form new carbon-centered radicals primed for nickel-catalyzed cross-couplings. Mechanistic experiments support the fact that the key radical components are formed independently, and relative rates are carefully orchestrated, such that no cross reactivity is observed.