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P-S Bond Formation

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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.


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.