Synthesis of Phosphorothioates

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In a Pd-catalyzed dehydrogenative phosphorylation, various thiols couple readily with H-phosphonates, H-phosphinates, and secondary phosphine oxides, to provide valuable phosphorothioates including P-chiral compounds. A plausible mechanism is proposed.
Y. Zhu, T. Chen, S. Li, S. Shimada, L.B. Han, J. Am. Chem. Soc., 2016, 138, 5825-5828.

With Ni(OAc)₂ as catalyst, an oxidative coupling of thiols and phosphonates to phosphorothioates with oxygen as oxidant proceeded very sluggishly with low yield, whereas adding non-redox-active metal ions such as Y³⁺ dramatically promoted the catalytic efficiency. Y(OTf)₃ can obviously accelerate the activation of thiols by Ni(II) and next accelerate its reaction with phosphonate.
J.-W. Xue, M. Zeng, S. Zhang, Z. Chen, G. Yin, J. Org. Chem., 2019, 84, 4179-4190.

Blue LED irradition promotes an environmentally friendly synthesis of phosphorochalcogenoates, phosphorochalcogenothioates, and phosphinothioates in very good yields under under metal-free, ligand-free, oxidant-free, and photocatalyst-free conditions with minimum chemical waste generation and high atom economy.
B.-R. Shen, P. Annamalai, S.-F. Wang, R. Bai, C.-F. Lee, J. Org. Chem., 2022, 87, 8858-8870.

A NaBr-catalyzed coupling reaction of Bunte salts with phosphonates enables a simple, green, and efficient synthesis of of thiophosphates in good yields in the presence of an acid and hydrogen peroxide (30%).
C. Min, R. Zhang, Q. Liu, S. Lin, Z. Yan, Synthesis, 2018, 50, 2027-2030.

Using L-proline as the ligand for a Cu-catalyzed coupling of sulfuryl chloride with P(O)-H compounds decreased the precatalyst loading, broadened the substrate scope and greatly promoted the efficiency of the coupling reaction. Moreover, gram-scale preparation, easy-to handle and recyclable catalyst featured this transformation.
X. Zhang, D. Wang, D. An, B. Han, X. Song, L. Li, G. Zhang, L. Wang, J. Org. Chem., 2018, 83, 1532-1537.

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.

A simple and efficient method for the preparation of thiophosphates from benzenethiols involves copper(I) iodide catalyzed coupling of thiols with H-phosphonates in the presence of triethylamine. The reaction proceeds effectively via an aerobic dehydrogenative coupling to afford the corresponding thiophosphates in good yields.
B. Kaboudin, Y. Abedi, J.-Y. Kato, T. Yokomatsu, Synthesis, 2013, 45, 2323-2327.

A convenient reaction of thiols with H-dialkyl phosphites in the presence of DMSO as both solvent and oxidant provides various phosphorothioates under transition-metal-free conditions. The reaction proceeds with formation of a disulfide intermediate followed by nucleophilic substitution with the dialkyl phosphite.
B. Kaboudin, P. Daliri, H. Esfandiari, F. Kazemi, Synlett, 2023, 34, 249-252.

Tetrabutylammonium iodide (TBAI) catalyzes an aerobic oxidative cross-dehydrogenative coupling (CDC) of sulfonyl hydrazides with secondary phosphine oxides in the presence of atmospheric oxygen. This metal-free, efficient and practical approach provides an array of diverse phosphinothioates in very good yields.
T. Liu, Y. Zhang, R. Yu, J. Liu, F. Cheng, Synthesis, 2020, 52, 253-262.