P-S Bond Formation
Recent Literature
Visible-light photoredox catalysis achieved a dehydrogenative coupling of
phosphines and thiophenols at room temperature. Key to this success is the use
of benzaldehyde as a soft oxidant, which avoids phosphine oxidation. Furthermore,
an unexpected dealkylative coupling of secondary and tertiary alkylphosphines
with thiophenols is observed.
X. Wang, C. Xia, L. Wu,
Org. Lett., 2020, 22, 7373-7377.
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.
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.
