Categories: C-S Bond Formation >
Synthesis of dithiocarbamates
A highly efficient, mild and simple synthesis of dithiocarbamates is based on the one-pot reaction of amines, CS2, and alkyl halides without using a catalyst under solvent-free conditions. The reaction is a highly atom-economic process for production of S-alkyl thiocarbamates.
N. Azizi, F. Aryanasab, M. R. Saidi, Org. Lett., 2006, 8, 5275-5277.
An efficient copper-mediated three-component coupling reaction of boronic acids, amines, and carbon disulfide provides a wide range of functionalized dithiocarbamates in very good yields. The method offers mild reaction conditions, easily available substrates, wide substrate scope, and high functional-group tolerance.
C. Qi, T. Guo, W. Xiong, Synlett, 2016, 27, 2626-2630.
An efficient transition-metal-free one-pot three-component reaction between diaryliodonium triflates, cyclic and acyclic aliphatic amines, and carbon disulfide provides biologically relevant S-aryl dithiocarbamates in good yields under mild conditions. This methodology is robust, scalable, and exhibits a broad substrate scope.
S. K. Parida, S. Jaiswal, P. Singh, S. Murarka, Org. Lett., 2021, 23, 6401-6406.
An efficient copper-catalyzed C(sp2)-S formation between aryl iodides and tetramethylthiuram monosulfide (TMTM) provides aryl dithiocarbamates in good to excellent yields. The high yields, decent functional group compatibility, and cost-effective substrates make this convenient protocol attractive for C-S bond formation.
Y.-X. Wu, K. Peng, J.-H. Li, Z.-B. Dong, Synthesis, 2020, 52, 3001-3006.
With only 1 mol% of CuCl2 as catalyst, zinc powder as reductant, and K2CO3 as base, a highly efficient C-S cross-coupling reaction of aryl iodides with tetraalkylthiuram disulfides provides dithiocarbamates in very good yields. This protocol has a broad substrate scope and uses cheap and readily available starting materials.
Q. Cao, H.-Y. Peng, Y. Cheng, Z.-B. Dong, Synthesis, 2018, 50, 1527-1534.
A copper-catalyzed preparation of aryl dithiocarbamates from aryl iodides and inexpensive, environmentally benign tetraalkylthiuram disulfides offers mild reaction conditions, high yields, and broad substrate scope. This approach is synthetically attractive for the preparation of potentially biologically active compounds.
Z.-B. Dong, X. Liu, C. Bolm, Org. Lett., 2017, 19, 5916-5919.
A green and efficient multicomponent reaction provides S-aryl dithiocarbamates without adding any transition-metal catalysts, ligands, or photocatalysts under visible light. This method provides a straightforward way to create valuable S-aryl dithiocarbamates while minimizing chemical wastes and metal residues in the end products.
G. Li, Q. Yan, Z. Gan, Q. Li, X. Dou, D. Yang, Org. Lett., 2019, 21, 7851-7856.
An efficient, ligand-free copper-catalyzed coupling of aryl iodides with tetraalkylthiuram disulfides in water provides a series of S-aryl dithiocarbamates in good yields.
X.-m. Wu, G.-b. Yan, Synlett, 2019, 30, 610-614.
A three-component coupling involving arynes, CS2, and aliphatic amines enables a facile synthesis of biologically important S-aryl dithiocarbamates. This transition-metal-free and mild reaction is scalable and operates with good functional group compatibility. With 3-triflyloxybenzyne, a unique four-component coupling incorporating tetrahydrofuran was observed.
S. Bhattarcharjee, S. Deswal, N. Manoj, G. Jindal, A. T. Biju, Org. Lett., 2021, 23, 9083-9088.
The reaction of diazonium tetrafluoroborates and diaryl dichalcogenides including sulfides, selenides and tellurides on the surface of alumina under ball-milling enables a convenient, efficient, and general synthesis of a wide range of diaryl chalcogenides in high purity without any solvent or metal.
N. Mukherjee, T. Chatterjee, B. C. Ranu, J. Org. Chem., 2013, 78, 11110-11114.
A mild, convenient, and practical one-pot procedure gives dithiocarbamates in good to excellent yields by condensation of amines, CS2, and a Michael acceptor, under solvent-free conditions at room temperature.
N. Azizi, F. Ebrahimi, E. Aakbari, F. Aryanasab, M. R. Saidi, Synlett, 2007, 2797-2800.
A facile photocatalyzed strategy for difunctionalization of styrenes in the presence of CS2 and amines provides β-keto dithiocarbamates. However, 4-nitrostyrene and 2-vinylpyridine can only be converted to 2-arylethylthiocarbamates.
R. K. Vishwakarma, S. Kumar, K. N. Singh, Org. Lett., 2021, 23, 4147-4151.