Photochemical Oximesulfonylation of Alkenes Using Sulfonyl‐Oxime‐Ethers as Bifunctional Reagents

Utilization of oxime ethers as bifunctional reagents remains unknown. Herein, we present a mechanistically distinct strategy that enables oximesulfonylation of olefins using sulfonyl‐oxime‐ethers as bifunctional reagents under metal‐free photochemical conditions. Via concomitant C−S and C−C bond formation, the process permits incorporation of oxime and sulfonyl groups into olefins in a complete atom‐economic fashion, providing rapid access to multi‐functionalized β ‐sulfonyl oxime ethers with good yields and stereoselectivity. The method is amenable to functionalization of complex bioactive molecules and is shown to be scalable. A radical chain mechanism initiated via photochemical Hydrogen Atom Transfer (HAT) mediated N−O bond cleavage is suggested for the process, based on our results on mechanistic investigations.