Synthesis and Reactivity of 3H-1,2-dithiole-3-thiones.

Oleg A Rakitin

doi:10.3390/molecules26123595

Abstract

3H-1,2-Dithiole-3-thiones are among the best studied classes of polysulfur-containing heterocycles due to the almost explosive recent interest in these compounds as sources of hydrogen sulfide as an endogenously produced gaseous signaling molecule. This review covers the recent developments in the synthesis of these heterocycles, including both well-known procedures and important novel transformations for building the 1,2-dithiole-3-thione ring. Diverse ring transformations of 3H-1,2-dithiole-3-thiones into various heterocyclic systems through 1,3-dipolar cycloaddition, replacement of one or two sulfur atoms to form carbon- and carbon-nitrogen containing moieties, and other unexpected reactions are considered.

Highlights

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The review covers the latest data on the synthesis and reactivity of 3H-1,2-dithiole-3thiones which have been intensely studied for about 150 years
The reason of the importance of these heterocycles in these days is that the 1,2-dithiole-3-thione moiety is present in a number of commercial drugs such as Oltipraz, Anethole dithiolethione, S-Danshensu, and NOSH-1

Summary

Introduction

1,2-Dithioles have been an important class of sulfur heterocycles since 1884, when the first representative of this class, 4,5-dimethyl-1,2-dithiole-3-thione (1) was synthesized [1]. 1,2-Dithiole derivatives show many types of significant pharmacological activity, including antitumor, antioxidant, chemotherapeutic, antithrombotic and radioprotective properties [2,3,4,5,6,7,8,9]. Treatment of N-methyl-2-methylindole with a fivefold excess of disalt obtained from disulfur dichloride (one equivalent) and DABCO (two equivalents) in chloroform at room temperature [67] followed by addition of triethylamine gave fused dithioloindole (R = Me) in high to moderate yields [68] Later, this reaction was extended to other N-substituted 2-methylindoles [69]. In the reaction of thione 11 with one equivalent of DMAD in the presence of scandium triflate (Sc(OTf)3), the addition product of one alkyne molecule 58 could be isolated in a low yield The latter was found to be unstable and decomposed back to thione 11 on storage (Scheme 40).

Reactions with Alkenes

3.11. Miscellaneous Reactions

Findings

Conclusions