- A green and efficient route for P ? S ? C bond construction using copper ferrite nanoparticles as catalyst: a TD-DFT study
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Magnetic nanoparticles of CuFe2O4 were applied as catalyst system for one-pot thiophosphate synthesis via the reaction of aryl sulfonyl chlorides with H-phosphonates under conventional heating conditions. This is an extremely efficient and green method for thiophosphate synthesis under base- and solvent-free conditions. Various thiophosphates were obtained in good to excellent yields under the optimized reaction conditions in a short time. The catalyst can be easily recycled from the reaction by an external magnetic field and reused for the next run. In this study, TD-DFT B3LYP/6-31 + G(d) calculations are in good accord with the experimental results. A comparison between experimental and theoretical UV-vis absorption spectra of the thiophosphate 3k has been carried out; and a small hypsochromic shift (only ~ 2 nm) was displayed at maximum absorption. The aim of this work is to investigate the best method and basis set for thiophosphate compounds; therefore, predictions for these compounds can be performed in theoretical studies.
- Moghaddam, Firouz Matloubi,Daneshfar, Maryam,Azaryan, Reza
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- Validation of Arylphosphorothiolates as Convergent Substrates for Ar-SF 4Cl and Ar-SF 5Synthesis
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In this manuscript we describe the oxidative fluorination of aryl phosphorothiolates to access Ar-SF4Cl compounds. These compounds serve as precursors for the highly coveted Ar-SF5 compounds. The use of phosphorothiolates as starting materials permits access to Ar-SF4Cl from a wide variety of available starting materials, namely boronic acids, diazonium salts, aryl iodides, thiophenols, or simple arenes. The protocol has been demonstrated for 10 examples and showed good tolerance to various functional groups. Finally, we demonstrated that AgBF4 can be used as a fluorinating agent, affording good yields of an Ar-SF5.
- Wang, Lin,Ni, Shengyang,Cornella, Josep
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supporting information
p. 4308 - 4312
(2021/06/02)
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- Electrochemically driven synthesis of phosphorothioates from trialkyl phosphites and aryl thiols
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A facile and elegant protocol for synthesis of phosphorothioates from trialkyl phosphites and aryl thiols via indirect electrochemical oxidation mediated by KI has been successfully developed. KI as a redox mediator, enabled the reaction of trialkyl phosp
- Guo, Xiaqun,Li, Meichao,Liu, Xin,Shen, Zhenlu,Shi, Shuxian,Wu, Zengzhi,Zhao, Lingmin
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- Synthetic method of thiophosphate compound
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The invention discloses a synthetic method of a phosphorothioate compound. The preparation method comprises the following steps: with thiol as a reaction substrate and trichloroisocyanuric acid (TCCA)as an accelerant, reacting the reaction substrate and the accelerant in an organic solvent at normal temperature and normal pressure for 10-20 minutes, then adding phosphite triester, continuing reacting for 10-20 minutes, and after the reaction is finished, carrying out separation treatment to obtain the phosphorothioate compound. According to the synthesis method disclosed by the invention, thereaction is carried out at normal temperature and normal pressure without special requirements; reaction time is short; and reaction substrate universality is good.
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Paragraph 0053-0054
(2020/05/30)
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- Trichloroisocyanuric acid-promoted thiolation of phosphites by thiols
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A simple and convenient method for the synthesis of thiophosphates by coupling of phosphites with thiols under mild conditions has been developed. The reactions were promoted by trichloroisocyanuric acid (TCCA) and were carried out at room temperature in
- Chen, Yingying,Li, Meichao,Gong, Zhangshui,Shen, Zhenlu
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- Lewis Acid Promoted Aerobic Oxidative Coupling of Thiols with Phosphonates by Simple Nickel(II) Catalyst: Substrate Scope and Mechanistic Studies
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Exploring new catalysts for efficient organic synthesis is among the most attractive topics in chemistry. Here, using Ni(OAc)2/LA as catalyst (LA: Lewis acid), a novel catalyst strategy was developed for oxidative coupling of thiols and phosphonates to phosphorothioates with oxygen oxidant. The present study discloses that when Ni(OAc)2 alone was employed as the catalyst, the reaction proceeded very sluggishly with low yield, whereas adding non-redox-active metal ions such as Y3+ to Ni(OAc)2 dramatically promoted its catalytic efficiency. The promotional effect is highly Lewis acidity dependent on the added Lewis acid, and generally, a stronger Lewis acid provided a better promotional effect. The stopped-flow kinetics confirmed that adding Y(OTf)3 can obviously accelerate the activation of thiols by Ni(II) and next accelerate its reaction with phosphonate to generate the phosphorothioate product. ESI-MS characterizations of the catalyst disclosed the formation of the heterobimetallic Ni(II)/Y(III) species in the catalyst solution. Additionally, this Ni(II)/LA catalyst can be applied in the synthesis of a series of phosphorothioate compounds including several commercial bioactive compounds. This catalyst strategy has clearly supported that Lewis acid can significantly improve the catalytic efficiency of these traditional metal ions in organic synthesis, thus opening up new opportunities in their catalyst design.
- Xue, Jing-Wen,Zeng, Miao,Zhang, Sicheng,Chen, Zhuqi,Yin, Guochuan
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p. 4179 - 4190
(2019/04/30)
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- Synthetic method for phosphorothiolate compounds
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The invention discloses a synthetic method for phosphorothiolate compounds, and the reaction steps of the synthetic method are as follows: dissolving diaryl disulfide in the solution, taking oxygen inthe air as an oxidizing agent, stirring at room tempera
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Paragraph 0007; 0050-0052
(2018/12/01)
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- Reactions of Disulfides with Silyl Phosphites to Generate Thiophosphates Under Neat Conditions
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An efficient procedure for the synthesis of thiophosphates is described. Without using any metallic catalyst or base, the direct sulfur–phosphorus coupling reaction of disulfides and dialkyl trimethylsilyl phosphite (DTSP) was carried out under solvent-fr
- Zhan, Zhen,Yang, Zhongzhen,Ma, Dena,Zhang, Hao,Shi, Yuesen,Wang, Qiantao,Deng, Yong,Hai, Li,Wu, Yong
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p. 1426 - 1431
(2018/05/22)
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- Base-controlled Fe(Pc)-catalyzed aerobic oxidation of thiols for the synthesis of S-S and S-P(O) bonds
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Fe(Pc)-Catalyzed aerobic oxidation of thiols for the synthesis of disulfides has been developed under mild reaction conditions. In addition, an aerobic oxidative cross-dehydrogenative coupling (CDC) reaction of thiols with P(O)-H compounds (H-phosphonates and H-phosphine oxide) for the formation of S-P(O) bonds has been demonstrated under the Fe(Pc) catalysis system with a base additive. Control experiments revealed that the use of a base (DIPA) in this system controls the synthetic pathways in which thiophosphates are formed.
- Huang, Hai,Ash, Jeffrey,Kang, Jun Yong
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p. 4236 - 4242
(2018/06/21)
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- K2CO3-promoted aerobic oxidative cross-coupling of trialkyl phosphites with thiophenols
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Convenient, practical and economical phosphorylation of thiols has been achieved via halogen- and metal-free K2CO3-promoted aerobic oxidative cross-coupling of trialkyl phosphites, dimethyl phenylphosphonite, or methyl diphenylphosphinite with thiophenols using air as the oxidant at room temperature. This transformation provides a straightforward route to the construction of phosphorus-sulfur bonds with wide functional group compatibility, which affords phosphorothioates in up to 94% yield.
- Wen, Chunxiao,Chen, Qian,Huang, Yulin,Wang, Xiaofeng,Yan, Xinxing,Zeng, Jiekun,Huo, Yanping,Zhang, Kun
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p. 45416 - 45419
(2017/10/06)
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- Iodine-catalyzed sulfenylation of H-phosphonates with diaryl disulfides under metal, base and solvent-free conditions
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Background: Although the exploitation of facile and efficient preparation for S-aryl phosphorothioates has gained considerable interest, there is still great demand for the development of a direct, convenient and especially environmentally benign protocol
- Wu, Xiang-Mei,Hong, Yu-Xiang
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- Cs2CO3-Catalyzed Aerobic Oxidative Cross-Dehydrogenative Coupling of Thiols with Phosphonates and Arenes
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An efficient Cs2CO3-catalyzed oxidative coupling of thiols with phosphonates and arenes that uses molecular oxygen as the oxidant is described. These reactions provide not only a novel alkali metal salt catalyzed aerobic oxidation, but also an efficient approach to thiophosphates and sulfenylarenes, which are ubiquitously found in pharmaceuticals and pesticides. The reaction proceeds under simple and mild reaction conditions, tolerates a wide range of functional groups, and is applicable to the late-stage synthesis and modification of bioactive molecules.
- Song, Song,Zhang, Yiqun,Yeerlan, Adeli,Zhu, Bencong,Liu, Jianzhong,Jiao, Ning
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supporting information
p. 2487 - 2491
(2017/02/23)
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- A thiophosphate synthetic method of compound and the method in a plurality of pharmaceutical application in the synthesis of (by machine translation)
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The invention discloses a having the general formula (III) of the thiophosphate synthetic method of compound, the purpose is to provide a novel, condition is simple, easy to industrial production of the thiophosphate synthetic method of compound. The method is to have the general formula (I) of the organophosphorus oxygen apperception compound having the general formula (II) with a mercaptan or phenyl-sulfhydryl apperception compound mixed, under the effects of catalyst, obtained by the reaction of the formula (III) of the thiophosphate compound. The method of the invention, can be cheap efficient synthesis of thiophosphate compounds, in actual production will have extensive application prospect. (by machine translation)
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Paragraph 0203; 0204; 0205; 0206
(2017/07/20)
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- Synthesis of S-Aryl Phosphorothioates by Copper-Catalyzed Phosphorothiolation of Diaryliodonium and Arenediazonium Salts
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Green methods for the synthesis of S-aryl phosphorothioates have been developed based on copper-catalyzed multicomponent reactions involving diaryliodonium/arenediazonium salts, elemental sulfur, and R2P(O)H compounds. Most target products are obtained with these two methods in good to high yields at room temperature. These transformations allow the direct formation P-S and C-S bonds in one reaction.
- Zhang, Liangliang,Zhang, Pengbo,Li, Xueqin,Xu, Jian,Tang, Guo,Zhao, Yufen
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p. 5588 - 5594
(2016/07/13)
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- Peroxide promoted metal-free thiolation of phosphites by thiophenols/disulfides
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A metal-free oxidative P-S bonds coupling method for the synthesis of thiophosphates with DTBP as the oxidant is established. A wide range of functionalities are tolerated in the method. This method provides a facile way to synthesize thiophophates from readily available thiophenols/disulfides and phosphites.
- Wang, Jichao,Huang, Xin,Ni, Zhangqin,Wang, Sichang,Pan, Yuanjiang,Wu, Jun
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p. 7853 - 7859
(2015/09/15)
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- Copper(I)-induced sulfenylation of H-phosphonates, H-phosphonites and phosphine oxides with aryl/alkylsulfonylhydrazides as a thiol surrogate
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Aerobic dehydrogenative sulfenylation of H-phosphonites, and phosphine oxides with aryl/alkylsulfonyl hydrazides catalyzed by a sub-stoichiometric amount of copper iodide has been accomplished. This protocol is compatible with functional groups, and results in various thiophosphate derivatives in good to high yields.
- Kumaraswamy, Gullapalli,Raju, Ragam
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p. 2591 - 2598
(2014/09/29)
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- Copper(I) iodide catalyzed synthesis of thiophosphates by coupling of H -phosphonates with benzenethiols
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A simple, efficient, and new method has been developed for the preparation of thiophosphates from benzenethiols. The method involves copper(I) iodide catalyzed coupling of thiols with H-phosphonates in the presence of triethylamine. The reaction proceeds effectively to afford the corresponding thiophosphates in moderate to good yields via an aerobic dehydrogenative coupling of H-phosphonates with benzenethiols. This method is easy, rapid, and good-yielding for the synthesis of thiophosphates from benzenethiols. Georg Thieme Verlag Stuttgart. New York.
- Kaboudin, Babak,Abedi, Yaghoub,Kato, Jun-Ya,Yokomatsu, Tsutomu
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p. 2323 - 2327
(2013/09/02)
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