Tunable Photocatalytic Oxysulfonylation and Chlorosulfonylation of α-CF3 Alkenes with Sulfonyl Chlorides

Tunable photoredox-catalyzed chlorosulfonylation and oxysulfonylation of α-trifluoromethylstyrenes with sulfonyl chloride were facilely achieved by simply manipulating photocatalyst and solvent. This strategy makes full use of the structural features of sulfonyl...

SULFONYL CHLORIDES - NOVEL SOURCE OF FREE RADICALS

Novel free radicals source based on sulfonyl chlorides is discovered. The radical mechanism is confirmed by 2,3-dimethyl-2,3-diphenylbutane formation under chlorosulfonated polyethylene heating in the isopropylbenzene solution. Concerted homolytic C-S and S-Cl bond scission of chlorosulfonated polyethylene thermal degradation mechanism proved by kinetic analysis. The proof of the two bonds simultaneous breaking is provided by the threefold activation energy reduction (83 kJ/mol) in comparison to the C-S and C-Cl bond dissociation energy (280 and 286 kJ/mol respectively), the 6 orders lower preexponential factor (2,46 ∙ 10 s) in Arrhenius equation in comparison to one bond cleavage (≈10-10 s) as well as the strongly negative activation entropy value (-134 J/mol∙K).

Facile Synthesis of Sulfonyl Chlorides/Bromides from Sulfonyl Hydrazides

A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazide with NXS (X = Cl or Br) and late-stage conversion to several other functional groups was described. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides and sulfonates. In most cases, these reactions are highly selective, simple, and clean, affording products at excellent yields.

Facile Synthesis of Sulfonyl Chlorides/Bromides from Sulfonyl Hydrazides

A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazide with NXS (X = Cl or Br) and late-stage conversion to several other functional groups has been described. A variety of nucleophiles could be engaged in this transformation thus permitting the synthesis of complex sulfonamides, sulfonates. In most cases, these reactions are highly selective, simple, and clean, affording products in excellent yields.