Electrochemical Formation of 3,5-Diimido-1,2-dithiolanes by Dehydrogenative Coupling

Abstract

A synthetic approach to the cyclic disulfide moiety of 3,5-diimido-1,2-dithiolane derivatives starting with readily available precursors including the electrochemical coupling of dithioanilides is developed. The electrochemical key step provides sustainable synthetic access in high yields, using a very simple electrolysis setup.

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

“…Waldvogel and co-workers reported an electrochemical method enabling dehydrogenative S–S bond formation in an intramolecular cyclization reaction of dithioanilides, giving 3,5-diimido-1,2-dithiolanes. 278 Optimized reaction conditions involved constant current electrolysis of substrates in an undivided cell equipped with graphite anode, Pt cathode, n -Bu 4 N + PF 6 – supporting electrolyte in MeOH solution ( Scheme 78 ). A scope of 12 examples of dehydrogenative S–S bond formation were reported, including both symmetrical ( 78.1 ) and unsymmetrical ( 78.2 ) dithioanilides (33–87% yields).…”

N,N′-Diphenyldithiomalonodiamide: Structural Features, Acidic Properties, and In Silico Estimation of Biological Activity

“…Dithiomalonodiamides and, in particular, N,N'diphenyldithiomalonodiamide 1 are actively used in various chemistry fields as bidentate complexing agents [1][2][3][4][5][6], steel corrosion inhibitors [7], reagents for the Ag + extraction from chloride-containing aqueous solutions [8], and also as starting reagents for the synthesis of a number of sulfur-containing heterocyclic systems-derivatives of 1,2-dithiol [9][10][11][12][13][14], thiazole [15,16], 1,3-dithiine [17][18][19][20][21][22], [1,2]dithiolo [3,4-b]pyridine [23], 1,2,3-thiadiazole [24], thiophene [25,26], 3,5-diaminopyrazole [11,26,27], etc. (Scheme 1).…”

Electrifying green synthesis: recent advances in electrochemical annulation reactions

“…Waldvogel and co-workers also reported an electrochemical approach for S-S coupling of dithioanilines 137, providing the cyclic 3,5-diimido-1,2-dithiolane derivatives 138 with yields of up to 89%, tolerating various groups of substituents (Scheme 37). 153 In 2016, the same authors proposed a method for access to pyrazolidin-3,5-diones through anodic N-N bond formation. 150 Additionally, in 2018, the group developed an electrochemical conversion of phthaldianilides to phthalazin-1,4-diones by dehydrogenative N-N bond formation.…”