Direct Photoinitiated Bromosulfonylation of Alkenes and Alkynes

The reaction of direct photoinitiated bromosulfonylation of alkynes and alkenes with p‐tolylsulfonyl bromide is reported. Low‐power radiation with a maximum wavelength of 400 nm is used for the reaction. The reaction proceeds at room temperature under metal‐free conditions. A photocatalytic bisimine additive is proposed that significantly increases the stereoselectivity of the alkyne bromosulfonylation reaction and increases the yield of products. The reaction scope is demonstrated with 49 examples. Methods for the subsequent functionalization of β ‐bromovinylsulfones to obtain valuable products are proposed.