NaHSO₃‐Mediated Direct Synthesis of Sulfinic Esters from Sulfonyl Hydrazides under Transition‐Metal‐Free Conditions

Abstract

We have developed a protocol for the NaHSO3‐promoted esterification of sulfonyl hydrazides with alcohols for the synthesis of sulfinic esters. Various sulfonyl hydrazides could be converted to the corresponding sulfinic esters in good to high yields. The merits of this protocol include mild transition‐metal‐free reaction conditions, an inexpensive and available reagent, and operational simplicity. Controlled experiments reveal that this transformation probably undergoes via a radical pathway.

Controllable synthesis of disulfides and thiosulfonates from sodium sulfinates mediated by hydroiodic acid using ethanol and H2O as solvents

“…3 Numerous methods have been developed previously to address the unmet challenges for using disulfides and thiosulfonates because of their widespread applications. 3 In recent years, the oxidation of thiols was frequently employed for the synthesis of disulfides and thiosulfonates, 4,5 especially using visible-light irradiation or electrochemical approaches. Li and co-workers reported a simple and efficient photocatalytic method for the virtually quantitative and selective conversion of thiols into disulfides by visible-light irradiation of CdSe-QD/thiolate conjugates.…”

Synthesis of Trifluoromethylated Pyrazolidines, Pyrazolines and Pyrazoles via Divergent Reaction of β-CF3-1,3-Enynes with Hydrazines

“…In the absence of AgNO 3 , the reaction could not occur either, even at increased temperature (Table , entry 2). Screening literature revealed that sulfonyl hydrazines can be utilized as sulfonyl sources, aryl sources, and sulfenyl sources through the cleavage of their S–N bonds, C–S bonds, or S–O and S–N bonds, respectively, under proper oxidation conditions or at an elevated temperature, which will compete with the desired hydroamination reaction. Hence, in order to avoid the above-mentioned undesired transformation, common used transition-metal catalysts that can enhance the electrophilicity of the enynes cannot be used in the present hydroamination reaction, because of their potential oxidation properties, we then have a tendency to find proper base additives for our desired transformation.…”

2-Acetamido-2-deoxy-d-glucono-1,5-lactone Sulfonylhydrazones: Synthesis and Evaluation as Inhibitors of Human OGA and HexB Enzymes

“…p-Toluenesulfonyl hydrazide (2a) was purchased from Sigma-Aldrich Ltd. (Budapest, Hungary). 2-Acetamido-3,4,6-tri-O-acetyl-2-deoxyα,β-D-glucopyranose (1) [16,17], substituted benzenesulfonyl hydrazides (2b-d), and 2-or 1-naphthalenesulfonyl hydrazides (2e-f) [18] were synthesized according to literature procedures. Unless otherwise indicated, all chemicals used in the biochemical experiments were of analytical grade and were purchased from Sigma-Aldrich Ltd. (Budapest, Hungary).…”

“…The starting material 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-D-glucopyranose (1) was obtained from D-glucosamine hydrochloride by a well-known two-step procedure [16,17] in 83% overall yield. Compound 1 was then converted by arenesulfonyl hydrazides 2 (either commercial or obtained from the corresponding arenesulfonyl chloride as described in the literature [18]) in the presence of 10 mol% p-toluenesulfonic acid catalyst in chloroform to afford N-glycosyl arenesulfonyl hydrazides 3. The oxidation reactions to yield lactone hydrazones 4 were carried out with activated MnO 2 in dichloromethane at reflux temperature.…”