Electrochemical synthesis of carbamo(dithioperoxo)thioates through the dehydrogenation coupling of thiols and amines and the insertion of CS₂

Abstract

A convenient and practical strategy was developed for the synthesis of carbamo(dithioperoxo)thioates through the simple dehydrogenation coupling of thiols and amines and the insertion of CS2 under mild reaction conditions...

Electrochemically driven α-thiocarbamylation via a dehydrocoupling strategy of β-ketoesters with amines and CS2

“…Based on the above studies and previous reports, 7,8 we proposed a possible reaction mechanism using 1a , CS 2 and 2a as model substrates (Scheme 5). First, the dehydrogenation reaction of CS 2 and 2a under alkaline conditions forms the dithiocarbamate anion, which is activated by anodic oxidation to form the dithiocarbamate cation, followed by the rapid electrostatic generation of the major intermediate 5 .…”

“…However, this impossible reaction is now smoothly achieved by halogen/halide/electrochemical mediation with the S/O-centered nucleophilic compound mercaptan/benzyl alcohol (Scheme 1a). 8 On the other hand, Liang developed a C–S bond coupling reaction of CS 2 and amines with active methylene compounds mediated by CBr 4 , but it required anhydrous solvents for its success and had limited application due to complex synthetic pathways and environmental concerns associated with halide reprocessing (Scheme 1b). 9 As a result, green and efficient synthesis methods with good atom economy under mild reaction conditions have become a main research direction for the construction of sulfur-containing compounds.…”

Electrochemical Difunctionalization of Alkenes: Simultaneous Construction of C–Se and C–S Bonds

“…Based on the above experiments and previous reports, 11 the possible mechanism for the formation of target product 4 is described in Scheme 3b. First, CS 2 and 3a are dehydrogenated under basic conditions to generate a dithiocarbamate anion (E p = 0.09 V and 1.13 V vs Ag/AgCl).…”

Effective Electrochemical Synthesis of an Important Fungicide Tetramethylthiuram Disulfide and Its Bioactive Analogues

“…50,51 Recently, electrochemical synthesis of carbamo(dithioperoxo)thioates synthesized in an undivided electrochemical cell was proposed. 52 Its conditions were applied for the electrosynthesis of tetraethylthiuram disulfide, but its yield was quite moderate. Thus, known electrochemical methods for the synthesis of TMTD or its analogues either require a complicated three-electrode cell or use preprepared dithiocarbamates or give the target compound in a moderate (50%) yield.…”