Synthesis of Phenyl Dithiocarbamates Starting from Sodium Dialkyldithiocarbamates and Aryl Boronic Acids: a Copper Catalyzed S‐Arylation

Abstract

A convenient and efficient protocol for the S‐arylation of sodium dialkyldithiocarbamates was developed. With the catalysis of copper(I) bromide, sodium dialkyldithiocarbamates coupled with aryl boronic acids giving the C‐S coupling products smoothly in good to excellent yields. This protocol features easily available starting materials, easy performance, short reaction time, broad substrate scope and good yields, showing its potential synthetic value for the convenient preparation of some potentially biologically active compounds.

Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

“…This approach has been further extended to the synthesis of technologically important ternary and quaternary sul- Copper dithiocarbamates have not found widespread use in homogeneous catalysis, despite having many of the attributes associated with good catalysts such as a range of accessible oxidation states and coordinative unsaturation. While the reaction discussed above is formally catalytic, the amounts of copper used are near to stoichiometric; nevertheless, there soon followed a range of related transformations in which much smaller amounts of copper were utilised either in the presence of dithiocarbamates [313,314] or thiuram disulfides [315][316][317][318]. By way of example, Bolm and co-workers have reported that Cu 2 O is an efficient catalyst for the formation of aryl dithiocarbamates from the coupling of thiuram disulfides and aryl iodides [315].…”

A Chemoselective and Desulfurative Chan–Lam Coupling: C–N Bond Formation between Benzimidazoline‐2‐Thiones and Arylboronic Acids

“…On the other hand, it is known that desulfurative couplings, such as the Liebeskind reaction or the Suzuki–Miyaura reaction, are generally performed under harsh reaction conditions, which usually involve the use of expensive transition metal catalysts and ligands, high temperature, as well as the use of inert atmosphere for the construction of C–C bonds . As part of our longstanding interest in heterocyclic chemistry and organosulfur chemistry in the development of Chan–Lam couplings, we herein disclose a chemoselective and desulfurative Chan–Lam coupling which affords C–N formation products ( N ‐arylbenzimidazoles, Scheme ) starting from benzimidazoline‐2‐thiones and arylboronic acids. The selectivity can be controlled by modulating the amount of Cu(OAc) 2 · H 2 O, base, temperature and solvent, which could provide attractive and alternative approach to access these important compounds.…”

Progress in Photoinduced Radical Reactions using Electron Donor‐Acceptor Complexes

“…Among of sulfur‐containing compounds, organic dithiocarbamates are important biologically active molecules [145] . Traditional methods for the synthesis of dithiocarbamates require toxic metal salt catalysts, unavailable precursors under harsh reaction conditions [146,147] . In 2019, Yang's group developed a green and efficient visible light‐induced multicomponent reaction of aryl halides, CS 2 and amines for the synthesis of S ‐aryl dithiocarbamates (Scheme 46).…”

“…[145] Traditional methods for the synthesis of dithio-carbamates require toxic metal salt catalysts, unavailable precursors under harsh reaction conditions. [146,147] In 2019, Yang's group developed a green and efficient visible lightinduced multicomponent reaction of aryl halides, CS 2 and amines for the synthesis of S-aryl dithiocarbamates (Scheme 46). [148] The reaction has the advantages of mild conditions, good functional group tolerance and catalyst-/ ligand-free.…”