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Dual Semiconductor‐Photoredox/Halogen‐Bonding Organocatalyzed Cascade Sulfonylation/Cyclization of Alkynes and Alkenes with RSO <sub>2</sub> Cl

Yaohui Wang, Lei He, Yuyu Tan, Z. H. Zhang, Yao‐Dan Xu, Rou Ding, Jun Jiang, Wei‐Min He

2025Advanced Science8 citationsDOIOpen Access PDF

Abstract

Abstract The dual semiconductor‐photoredox/halogen‐bonding organocatalyzed cascade sulfonylation/cyclization of (hetero)arene‐tethered alkynes and alkenes with RSO 2 Cl is first developed. This method proceeds efficiently under mild reaction conditions, delivering a variety of sulfonylated fused‐(hetero)arenes with good functional group compatibility. Mechanistic investigations reveals that XantPhos interacts with RSO 2 Cl to form a halogen‐bonding complex, which facilitates S─Cl bond cleavage under blue light irradiation. Specifically, the Sr 3 N 2 semiconductor catalyst promotes heterolytic S─Cl bond cleavage through a SET process, generating a sulfonyl radical and chloride ion. In contrast, the sulfonylated fused‐(hetero)arene facilitates homolytic S─Cl bond cleavage via an EnT pathway, proudcing a sulfonyl radical.

Topics & Concepts

ChemistryHeterolysisHomolysisBond cleavageCatalysisSulfonylCleavage (geology)Combinatorial chemistryCascade reactionCascadeXantphosChloridePhotochemistryFunctional groupTriple bondOrganocatalysisOrganic chemistryMedicinal chemistryDual (grammatical number)Reaction conditionsStereochemistryDual roleSulfur-Based Synthesis TechniquesRadical Photochemical ReactionsCatalytic C–H Functionalization Methods