Categories: C-S Bond Formation >
Synthesis of phosphorothioates
The use of the iminium salt prepared from N,N-dimethylthioformamide and Meerwein’s salt enables a direct and rapid conversion of primary and secondary alcohols to the corresponding phosphorothiolates in good yields. Selective reaction of primary alcohols in the presence of secondary alcohols is possible. The reaction of secondary alcohols proceeds stereospecifically with inversion of configuration.
H. Grounds, K. Ermanis, S. A. Newgas, M. J. Porter, J. Org. Chem., 2017, 82, 12735-12739.
An Ir-catalyzed decarboxylative phosphorothiolation of N-hydroxyphthalimide esters provides phosphorothioates under visible light irradiation. The reaction tolerates a broad range of functional groups, provides sterically hindered phosphorothioates, and enables the late stage modification of bioactive molecules.
Y. Guo, Y. Luo, S. Mu, J. Xu, Q. Song, Org. Lett., 2021, 23, 6729-6734.
The use of diaryliodonium salts enables a direct metal-free S-arylation of phosphorothioate diesters. The method allows for the preparation of a broad range of S-aryl phosphorothioates as well as other related organophosphorus compounds under simple conditions. The reaction proceeds with a full retention of the stereogenic center at the phosphorus atom.
S. Sarkar, M. Kalek, Org. Lett., 2023, 25, 671-675.
A multicomponent reaction involving aryl boronic acids, elemental sulfur, and P(O)H compounds provides valuable S-aryl phosphorothioates and S-aryl phosphorodithioates in excellent yields. Moreover, this method can be easily scaled up.
J. Xu, L. Zhang, X. Li, Y. Gao, G. Tang, Y. Zhao, Org. Lett., 2016, 18, 1100-1103.
Green methods based on copper-catalyzed multicomponent reactions enable the synthesis of S-aryl phosphorothioates from diaryliodonium/arenediazonium salts, elemental sulfur, and R2P(O)H compounds in very good yields at room temperature. These transformations allow the direct formation of P-S and C-S bonds in one reaction.
L. Zhang, P. Zhang, X. Li, J. Xu, G. Tang, Y. Zhao, J. Org. Chem., 2016, 81, 5566-5573.