Carbofunctionalization of Alkenes with Sulfoxonium Ylides through Visible‐Light‐Induced Copper/Photoredox Dual Catalysis

Comprehensive Summary Radical‐mediated difunctionalization of alkenes has attracted intensive attention from the synthetic community in recent years. Carbon radicals play a pivotal role as reactive intermediates in alkene difunctionalization reactions, showcasing remarkable potential in forging both carbon‐carbon and carbon‐heteroatom bonds. Traditionally, these transformations proceed through the merger of the classical transition metal catalysis, employing metals such as Ag, Ni, Fe, Cu, and among others. Recently, photoredox catalysis has emerged as a powerful tool for enabling challenging molecular transformations and accessing previously inaccessible chemical space in an environmentally benign and mild manner. In the present work, a novel visible‐light‐induced copper/photoredox dual catalysis for intermolecular multicomponent difunctionalization of alkenes with aqueous sulfoxonium ylides and versatile functional groups has been developed. This reaction system utilizes alkenes and sulfoxonium ylides as easily prepared starting materials, operates under facile and sustainable conditions, and does not require the addition of acids or bases. Furthermore, the scalable protocol allows for the incorporation of a wide array of alkenes, sulfoxonium ylides, and external protic nucleophiles, including water, chloride, bromide, azide, and thiol. The general system provides a viable access to structurally C(sp 3 )‐rich γ‐hydroxylketones, organic halides, organic sulfides, and azide compounds with excellent chemo‐ and regioselectivity. Mechanistic investigations imply that two distinct reaction pathways are involved in the generation of carbon radicals from sulfoxonium ylides through a mild visible‐light‐driven proton‐coupled electron transfer (PCET) strategy in the absence or presence of copper salts. This dual catalytic system will establish a novel paradigm, thereby expanding the scope of carbon radical‐mediated transformations of olefins.