Sulfoximidation of Aryl Alkenes <i>via</i> Oxidative CC Bond Cleavage

KI−mediated cross‐coupling between aryl alkenes and NH −sulfoximines under base‐ and metal‐free reaction conditions has been developed. This process involves the sequential oxidative cleavage of the CC double bond, followed by CN bond formation to synthesize biologically relevant N ‐acyl sulfoximines. This protocol features a broad substrate scope, excellent functional group compatibility, and high yields. Mechanistic investigations indicate the intermediacy of benzaldehyde‐derived as an acyl radical and highlight the crucial role of atmospheric oxygen as the oxygen source.