Electrochemically driven synthesis of phosphorothioates from trialkyl phosphites and aryl thiols

Zhao, Lingmin; Liu, Xin; Shi, Shuxian; Wu, Zengzhi; Guo, Xiaqun; Shen, Zhenlu; Li, Meichao

doi:10.1016/j.electacta.2021.138748

Cited by 4 publications

(5 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…66 In 2021, with catalytic amount of KI as a redox mediator, an electrochemical synthesis of phosphorothioates 70 from trialkyl phosphites 71 and aryl thiols 58 was developed by the same group (Scheme 29b). 67 A wide substrate scope, including aryl, heteroaromatic and benzyl mercaptan 58 were compatible in this process. While using aliphatic thiols as substrate, only trace product was detected.…”

Section: Template For Synthesis Thiemementioning

confidence: 98%

Progress in S–X Bond Formation by Halogen-Mediated Electrochemical Reactions

Gui

2023

Synthesis

View full text Add to dashboard Cite

Sulfur-containing compounds are one of the most common and important heteroatom skeletons and are widely found in natural products, pharmaceuticals and bioactive compounds. Moreover, the development of the synthetic routes to organosulfur compounds have attracted a considerable attention due to their widely application in organic chemistry, pharmaceutical industry and materials science. As one of most powerful, green and eco-friendly research areas, organic electrosynthesis could avoid the use of harmful stoichiometric external oxidants or reductants, compared with conventional organic synthesis. Importantly, halide salts are widely used as supporting electrolyte and redox catalysts in indirect electrosynthesis to avoid the limitations imposed by high overpotentials in direct electrosynthesis. In recent years, great progress has been made in the halogen-mediated electrosynthesis of organosulfur compounds. In this minireview, the scope, limitations and mechanisms of halogen-mediated electrochemical transformations of sulfur-containing compounds are presented and discussed.

show abstract

Section: Template For Synthesis Thiemementioning

confidence: 98%

Progress in S–X Bond Formation by Halogen-Mediated Electrochemical Reactions

Gui

2023

Synthesis

View full text Add to dashboard Cite

show abstract

“…Finally, the P-centered radical underwent a coupling reaction with the thiyl radical to afford the target product. Subsequently, Li and co-workers [50] disclosed a facile and elegant approach for the construction of Saryl thiophosphates 19 by electro-induced oxidative cross-coupling of trialkyl phosphites 78 and thiophenols 10 in the presence of KI as a redox mediator (Scheme 35). A series of S-aryl thiophosphates were smoothly obtained in good to excellent yields under mild conditions.…”

Section: Electro-induced Radical Transformation To Construct Sulfur-c...mentioning

confidence: 99%

Recent Advances in the Direct Synthesis of Sulfur‐Containing Organophosphorus Compounds via Radical Processes

et al. 2023

View full text Add to dashboard Cite

Phosphonothioates, phosphinothioates and phosphorothioates are regarded as an important class of sulfur‐containing organophosphorus compounds. Because of the unique P(O)S−R group, these compounds have important biological activities and thus have been widely used in the fields of pharmaceuticals and pesticides. In recent years, the development of sulfur‐containing organophosphorus compounds by radical processes has attracted considerable attention in organophosphorus chemistry. Along these lines, in this review, the recent advances in the synthesis of sulfur‐containing organophosphorus compounds were systematically summarized. According to the different ways of generating radicals during the formation process of phosphonothioates, phosphinothioates and phosphorothioates, these transformations can be divided into four categories: (1) Oxidant or metal‐free promoted radical transformation to fabricate sulfur‐containing organophosphorus compounds; (2) Copper‐catalyzed radical transformation to produce sulfur‐containing organophosphorus compounds; (3) Photo‐induced radical transformation to prepare sulfur‐containing organophosphorus compounds; (4) Electro‐induced radical transformation to derive sulfur‐containing organophosphorus compounds.

show abstract

“…Trialkyl phosphites, as a cheap and readily available phosphoruscontaining reagent, can also be applied into the synthesis of organophosphorus compounds. [40][41][42][43][44] In 2020, we developed an efficient approach for synthesis of thiophosphates by coupling of thiols with trialkyl phosphites under mild conditions promoted by trichloroisocyanuric acid (TCCA). 40 After that, we also reported an indirect electrooxidation method for synthesis of phosphorothioates from trialkyl phosphites and aryl thiols catalyzed by potassium iodide at a low potential.…”

mentioning

confidence: 99%

“…40 After that, we also reported an indirect electrooxidation method for synthesis of phosphorothioates from trialkyl phosphites and aryl thiols catalyzed by potassium iodide at a low potential. 44 Until now, we have made great efforts in organic electrochemical synthesis. [44][45][46][47][48][49] These meaningful works have laid a good foundation for us.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Electrosynthesis of C−3 Phosphorylated 2H-Indazoles from Trialkyl Phosphites and 2H-Indazoles

Liu¹,

Yin²,

Wu³

et al. 2022

J. Electrochem. Soc.

Self Cite

View full text Add to dashboard Cite

A facile and efficient direct electrochemical oxidation method for C−3 phosphorylation of 2H-indazoles with trialkyl phosphites as the phosphorylation reagents has been developed. Introducing electricity to the green and sustainable synthetic procedures allowed the reactions to be carried out under simple and mild conditions without any metal salts and additional oxidants. Electrochemical data showed that the cation radical species which were generated from the oxidation of 2H-indazoles were stabilized by 1,1,1,3,3,3-hexafluoro-2-propanol and could be captured by trialkyl phosphites effectively to form C−3 phosphorylated 2H-indazoles. In an undivided cell, a board range of functional groups on various substrates were well tolerated and the yield of the desired phosphorylated products was up to 84%. Moreover, a plausible mechanistic proposal involving radical pathway was established based on the results of cyclic voltammetry, in situ FTIR and control experiments.

show abstract

Electrochemically driven synthesis of phosphorothioates from trialkyl phosphites and aryl thiols

Cited by 4 publications

References 55 publications

Progress in S–X Bond Formation by Halogen-Mediated Electrochemical Reactions

Progress in S–X Bond Formation by Halogen-Mediated Electrochemical Reactions

Recent Advances in the Direct Synthesis of Sulfur‐Containing Organophosphorus Compounds via Radical Processes

Electrosynthesis of C−3 Phosphorylated 2H-Indazoles from Trialkyl Phosphites and 2H-Indazoles

Contact Info

Product

Resources

About