Facile Synthesis of Sulfonyl Chlorides/Bromides from Sulfonyl Hydrazides

Abstract

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.

Catalyst-free electrochemical sulfonylation of amines with sulfonyl hydrazide in aqueous medium

“…On the basis of the above experimental results and literature reports, 35–39 a plausible reaction mechanism was proposed, as shown in Scheme 3. Initially, ionic bromine was oxidized to bromine radical at the graphite anode.…”

“…Note that when 1a, 2a and n-Bu 4 NBr were added together, a slight red shift in the oxidation peak for both 1a and 2a ( purple curve) and a remarkable improvement in the catalytic current were observed, which indicated that n-Bu 4 NBr played a crucial role as a mediator in promoting the oxidation of substrates 1a and 2a to generate the desired product. On the basis of the above experimental results and literature reports, [35][36][37][38][39] a plausible reaction mechanism was proposed, as shown in Scheme 3. Initially, ionic bromine was oxidized to bromine radical at the graphite anode.…”

Electrochemical synthesis of sulfonyl fluorides from sulfonyl hydrazides

“…The sulfonyl hydrazide moiety has gained significant attention as a powerful sulfonyl source in organic synthesis because the hydrazide group can be readily released under various reaction conditions to provide the sulfonyl source; the subsequent reaction of the sulfonyl source with a variety of counterpart molecules affords the desired sulfonyl compounds, such as sulfones, sulfonates, sulfonamides, sulfonyl halides, and thiosulfonates. 7 Wang et al reported the synthesis of sulfonyl fluorides via the reaction of sulfonyl hydrazides and Selectfluor. 8 However, the use of an expensive fluoride source and the need for elevated reaction temperatures are disadvantageous.…”

Iodosulfonylation of [1.1.1]Propellane

“…[20][21][22] They are reported to give sulfonyl halides in the presence of halogenating reagents such as Nbromosuccinimide, N-chlorosuccinimide, and KI (Scheme 1A, path d). 23,24 Herein, we wish to disclose a one-pot disubstituted functionalization of [1.1.1]propellane utilizing sul-…”