Synthesis of Aza‐Heteroaromatic Dithiocarbamates via Cross‐Coupling Reactions of Aza‐Heteroaromatic Bromides with Tetraalkylthiuram Disulfides

Abstract

The preparation of various aza‐heteroaromatic dithiocarbamates from aza‐heteroaromatic bromides and tetraalkylthiuram disulfides is reported. The transformation provides a convenient procedure, with good yields and functional group tolerance to various important nitrogen‐containing heteroaromatic dithiocarbamates such as benzothiazole, quinoline, pyridine, and pyrazine motifs. This protocol allows the facile synthesis of some potential biologically active compounds.

Regioselective Synthesis of Sulfonyl-Containing Benzyl Dithiocarbamates through Copper-Catalyzed Thiosulfonylation of Styrenes

“…Consequently, significant progress has been achieved on this topic not only by transition-metal (copper, − , palladium, − , nickel, gold, rhodium, iron, silver, cobalt, manganese, and other metals)-catalyzed difunctionalization of alkenes but also under transition-metal-free conditions. Based on our ongoing interest in the development of new methods for the formation of C–S bond, , we envisioned whether both sulfonyl and dithiocarbamate groups could be introduced simultaneously into the styrenes to form the sulfonyl-containing benzyl dithiocarbamates by a single operation. Herein, we report our latest work on the copper-catalyzed thiosulfonylation of styrenes under simple conditions (Scheme c).…”

Metal-free, tert-butyl nitrite promoted C(sp2)–S coupling reaction: the synthesis of aryl dithiocarbamates and analysis of antimicrobial activity by ‘in silico’ and ‘in vitro’ methods for drug modification

“…1), are the typical representatives of the biologically active dithiocarbamates scaffolds than the other dithiocarbamates. 19,20 Due to their various unique activities, we are interested in synthesizing aryl dithiocarbamates.…”

“…Traditionally, these aryl dithiocarbamates were prepared using tetraalkylthiuram disulfides with Grignard reagents, organozinc, and organolithium reagents through C(sp 2 )-S bond formation using stoichiometric amounts of the reagents (Scheme 1a). [21][22][23] Aryl dithiocarbamates were also synthesised with the help of various types of aryl halides and diaryliodonium salts with the help of a transition metal catalyst in the presence of a strong base 20,[24][25][26][27] and by the reaction of tetraalkylthiuram disulfides with aryl boronic acids 28 and thiophenols 29 with the use of a copper catalyst and strong base (Scheme 1a). In addition, Ranu et al reported a solvent-free synthesis of S-aryl dithiocarbamates under mechanochemical conditions by the reaction of aryl diazonium fluoroborate, carbon disulfide, and secondary amines.…”

Metal‐Free Synthesis of S‐Aryldithiocarbamates: Aryl C−S Bond Formation at Room Temperature†

“…Various, copper catalysts are mainly used for the preparation of dithiocarbamates [14–16] . Nevertheless, reports on direct aromatic nucleophilic substitution by dithiocarbamate anion without any transition metal as a catalyst are scarce in literature and required either the presence of strong bases like Cs 2 CO 3 and NaH or at elevated temperatures [17,18] …”