Photocatalytic Redox-Neutral Alkoxysulfonylation of Alkenes

β-Alkoxy sulfones are important building blocks in organic synthesis. Herein, we report that <b>CBZ6</b> is an efficient redox-neutral photocatalyst for the highly effective alkoxysulfonylation of alkenes with sulfonyl chlorides. This process is enabled by the addition of a sulfonyl radical to an alkene to generate the benzyl radical. The following oxidation of the benzyl radical leads to the benzyl cationic intermediate, which is then captured by alkoxy anions.