Categories: C-S Bond Formation >
Synthesis of thiocarbamates
S-Alkyl thiocarbamates and S-alkyl O-alkyl carbonothioates were synthesized in good yields by solvent-assisted thiocarboxylation of amines or alcohols with carbon monoxide and sulfur under mild conditions (1 atm, 20 °C) in DMSO or DMF.
T. Mizuno, T. Iwai, Y. Ishino, Tetrahedron, 2005, 61, 9157-9163.
A mild and efficient Mitsunobu-based protocol has been developed for the synthesis of various S-alkyl thiocarbamates from the corresponding thiols and amines using gaseous carbon dioxide, in good to excellent yields.
D. Chaturvedi, N. Mishra, V. Mishra, Synthesis, 2008, 355-357.
Readily prepared carbamoylimidazolium salts act as efficient N,N-disubstituted carbamoylating reagents, as a result of the ‘imidazolium’ effect. The salts react with amines, thiols, phenols/alcohols, and carboxylic acids in high yields, without the need for subsequent chromatographic purification of the products, producing ureas, thiocarbamates, carbamates, and amides, respectively.
J. A. Grzyb, M. Shen, C. Yoshina-Ishii, W. Chi, R. S. Brown, R. A. Batey, Tetrahedron, 2005, 61, 7153-7175.
A convenient visible-light-induced reaction of isocyanides, thiols, and water under mild reaction conditions provides various thiocarbamates in good yields in the presence of cheap Rose Bengal as the photocatalyst.
W. Wei, P. Bao, H. Yue, S. Liu, L. Wang, Y. Li, D. Yang, Org. Lett., 2018, 20, 5291-5295.
Molecular iodine catalyzes a facile and practical synthesis of thiocarbamates in good yields from readily available sodium sulfinates, isocyanides, and water. The present methodology offers favorable functional group tolerance and the use of odorless sodium sulfinates.
P. Bao, L. Wang, H. Yue, Y. Shao, J. Wen, D. Yang, Y. Zhao, H. Wang, W. Wei, J. Org. Chem., 2019, 84, 2976-2983.
Direct reaction of isocyanides with sulfoxides affords thiocarbamic acid S-esters in very good yields. In addition, multicomponent reactions involving isocyanide, sulfoxide, and a suitable nucleophile provide a diverse range of sulfur-containing compounds, including isothioureas, carbonimidothioic acid esters, and carboximidothioic acid esters.
S. Wu, X. Lei, E. Fan, Z. Sun, Org. Lett., 2018, 20, 522-525.
A method for the synthesis of secondary thiocarbamates from readily available isocyanides and thiosulfonates with broad functional group tolerance proceeds under mild reaction conditions in isopropanol and is catalyzed by inexpensive sodium iodide.
P. Mampuys, Y. Zhu, S. Sergeyev, E. Ruijter, R. V. A. Orru, S. Van Doorslaer, B. U. W. Maes, Org. Lett., 2016, 18, 2808-2811.