Dual Roles of Rongalite: Reductive Coupling Reaction to Construct Thiosulfonates Using Sulfonyl Hydrazides

Abstract

A tunable and practical transformation of structurally diverse sulfonyl hydrazides into thiosulfonates in the presence of Rongalite (NaHSO₂·CH₂O) was developed. Transition-metal-free conditions, operational simplicity, and readily available reagents are the striking features of this protocol. It is the first example for the synthesis of thiosulfonates using sulfonyl hydrazides with the assistance of reductant. Additionally, the mechanistic studies revealed that this transformation probably undergoes via a reducing–coupling pathway.

Key words

sulfonyl hydrazides - Rongalite - thiosulfonates - transition-metal-free - reductive coupling

Publication History

Received: 21 July 2020

Accepted after revision: 04 September 2020

Article published online:
09 October 2020

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• 18 S-(p-Tolyl) 4-Methylbenzenesulfonothioate (2a): Typical Procedure A mixture of 1a (0.2 mmol), NaHSO₂·CH₂O (0.4 mmol, 47.2 mg), and benzotrifluoride (1.0 mL) in a 15 mL flask was heated at 80 °C under air for 5 h. The reaction mixture was cooled to room temperature, poured into H₂O (10 mL) and extracted with EtOAc (20 mL). The organic layers were dried over anhydrous Na₂SO₄, filtered, and concentrated in vacuo. The crude product was purified by column chromatography on silica gel (petroleum ether/EtOAc = 30:1) to yield 2a as a white solid; yield: 51mg (91%).¹H NMR (500 MHz, CDCl₃): δ = 7.47 (d, J = 8.3 Hz, 2 H), 7.29–7.20 (m, 4 H), 7.15 (d, J = 8.0 Hz, 2 H), 2.43 (s, 3 H), 2.39 (s, 3 H).¹³C NMR (126 MHz, CDCl₃): δ = 144.56, 142.01, 140.43, 136.45, 130.17, 129.33, 127.56, 124.56, 124.56, 21.63, 21.45. HRMS (EI-TOF): m/z calcd for C₁₄H₁₄O₂S₂: 278.0435; found: 278.0466.