Hydrosulfonylation of Alkenes with Sulfonyl Chlorides under Visible Light Activation

Abstract

Sulfonyl chlorides are inexpensive reactants extensively explored for functionalization, but never considered for radical hydrosulfonylation of alkenes. Herein, we report that tris(trimethylsilyl)silane is an ideal hydrogen atom donor enabling highly effective photoredox‐catalyzed hydrosulfonylation of electron‐deficient alkenes with sulfonyl chlorides. To increase the generality of this transformation, polarity‐reversal catalysis (PRC) was successfully implemented for alkenes bearing alkyl substituents. This late‐stage functionalization method tolerates a remarkably wide range of functional groups, is operationally simple, scalable, and allows access to building blocks which are important for medicinal chemistry and drug discovery.

Easy Access to Aliphatic Sulfonamides using Sulfamoyl Chlorides Under Visible Light Activation

“…Furthermore, sulfonyl chlorides have shown to be reactive under similar reaction conditions. 45 A plausible mechanism of the hydrosulfamoylation of electron-deficient alkenes is depicted in Figure 3. Upon irradiation with light, the generated excited triplet state Eosin Y* [E 1/2 red (PC*/PC •-) = + 0.83 V versus saturated calomel electrode (SCE)] should readily oxidize tris(trimethylsilyl)silane (TTMSS) [E ox (TTMSS/TTMSS •+ ) = + 0.73 V versus SCE] via single-electron transfer (SET).…”

Hydrofluoromethylation of alkenes with fluoroiodomethane and beyond

“…30 Since the pioneering work of Chatgilialoglu, 31 tris(trimethylsilyl)silane (TTMSS) has found ample applications as a powerful tool for mild radical generation via the activation of alkyl halides. [32][33][34][35][36] In addition, TTMSS has valuably complemented Giese-type reactions, a commonly exploited platform for late-stage functionalisation, by providing a suitable alternative to traditional toxic tin-based reagents. 37 This method offers the prospect of being applicable to a range of other halo-containing alkyl radicals, provided that competitive hydrogen atom abstraction with (TMS) 3 SiH does not occur prior to Giese addition.…”

Photoinduced C(sp3)–H sulfination empowers the direct and chemoselective introduction of the sulfonyl group

“…The sulfonyl group is one of the most important functional groups in organic synthesis, 1 materials science, 2 and medicinal chemistry. 3 However, methods are lacking for the direct installation of the sulfonyl group by harnessing the abundant aliphatic C–H bonds with high potential for a rapid build-up of the structural diversity.…”