- Electrochemical Enabled Cascade Phosphorylation of N?H/O?H/S?H Bonds with P?H Compounds: An Efficient Access to P(O)-X Bonds
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An electrochemical three component cascade phosphorylation reaction of various heteroatoms-containing nucleophiles including carbazoles, indoles, phenols, alcohols, and thiols with Ph2PH has been established. Electricity is used as the “traceless” oxidant and water and air are utilized as the “green” oxygen source. All kinds of structurally diverse organophosphorus compounds with P(O)-N/P(O)-O/P(O)-S bonds are assembled in moderate to excellent yields (three categories of phosphorylation products, 50 examples, up to 97 % yield). A tentative free radical course is put forward to rationalize the reaction procedure.
- Abdukader, Ablimit,Dong, Xiaojuan,Jin, Weiwei,Liu, Chenjiang,Wang, Bin,Wang, Ruige,Xia, Yu,Xue, Fei,Zhang, Yonghong
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supporting information
p. 14931 - 14935
(2021/10/06)
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- Tf2O/DMSO-Promoted P-O and P-S Bond Formation: A Scalable Synthesis of Multifarious Organophosphinates and Thiophosphates
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A Tf2O/DMSO-based system for the dehydrogenative coupling of a wide range of alcohols, phenols, thiols, and thiophenols with diverse phosphorus reagents has been developed. This metal- and strong-oxidant-free strategy provides a facile approach to a great variety of organophosphinates and thiophosphates. The simple reaction system, good functional-group tolerance, and broad substrate scope enable the application of this method to the modification of natural products and the direct synthesis of bioactive molecules and flame retardants.
- Shen, Jian,Li, Qi-Wei,Zhang, Xin-Yue,Wang, Xue,Li, Gui-Zhi,Li, Wen-Zuo,Yang, Shang-Dong,Yang, Bin
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supporting information
p. 1541 - 1547
(2021/04/05)
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- Preparation method of sulfur-containing phosphonate
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The invention provides a preparation method of phosphonate. The method is characterized in that a phosphonate compound is prepared through a reaction in an organic solvent by taking organic phosphine oxide and alcohol as substrates, and trimethylsilyl tri
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Paragraph 0046-0053; 0062-0065
(2021/06/23)
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- An Alternative Metal-Free Aerobic Oxidative Cross-Dehydrogenative Coupling of Sulfonyl Hydrazides with Secondary Phosphine Oxides
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An alternative metal-free, efficient and practical approach for the preparation of phosphinothioates is established via the aerobic oxidative cross-dehydrogenative coupling (CDC) of sulfonyl hydrazides with secondary phosphine oxides catalyzed by tetrabutylammonium iodide (TBAI) in the presence of atmospheric oxygen. The strategy provides an array of diverse phosphinothioates in good to excellent yields. Furthermore, two representative bioactive molecules are synthesized on up to gram scale by utilizing this method.
- Cheng, Feixiang,Liu, Jianjun,Liu, Teng,Yu, Rong,Zhang, Yanqiong
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p. 253 - 262
(2019/12/28)
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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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- Synthetic method of diphenyl thiophosphate compound
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The invention discloses a synthesis method of a diphenyl thiophosphate compound. The preparation method comprises the following steps: by taking thiophenol as a reaction substrate and trichloroisocyanuric acid (TCCA) as an accelerant, reacting the reaction substrate and the accelerant in an organic solvent under the conditions of normal temperature and normal pressure for 10 minutes, then adding alkoxy diphenyl phosphine, continuously reacting for 10 minutes, and after the reaction is finished, carrying out separation treatment to obtain the diphenyl thiophosphate compound. According to the synthesis method disclosed by the invention, the reaction is carried out at normal temperature and normal pressure without special requirements; the reaction time is short; and high product yield is achieved.
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Paragraph 0029-0030
(2020/05/01)
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- Preparation method of compound containing P-O bond or P-S bond
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The invention discloses a preparation method of a compound containing a P-O bond or a P-S bond. The method comprises the following steps: a compound containing hydroxyl or sulfydryl and a phosphorus reagent are taken as initial raw materials; then, the initial raw materials are put into an inert gas atmosphere; and under the action of trifluoromethanesulfonic anhydride (Tf2O) and dimethyl sulfoxide (DMSO), the compound containing hydroxyl or sulfydryl, the phosphorus reagent, the trifluoromethanesulfonic anhydride and the dimethyl sulfoxide in a molar ratio of (1-5): (1-2.5): (2-3): 2 react inan organic solvent at the reaction temperature of 25-100 DEG C for 6-20 hours to obtain the compound with the structural general formula (I). The reagents used in the method are low in toxicity and environmentally friendly, and use of precious metal catalysts high in price and toxicity is avoided. The reagents trifluoromethanesulfonic anhydride (Tf2O) and dimethyl sulfoxide (DMSO) used in the method are low in toxicity and very low in cost, so that the method is green, environment-friendly, high in economy and suitable for large-scale production.
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Paragraph 0055-0062
(2020/09/12)
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- Highly atom-economical, catalyst-free, and solvent-free phosphorylation of chalcogenides
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Silica gel promoted, catalyst-free and solvent-free S-P, Se-P and Te-P bond formations are described. A variety of disulfides coupled with diarylphosphine oxides provide the corresponding phosphinothioates in excellent yields. For the first time, diselenides and ditellurides reacted with dialkyl phosphites under catalyst-free conditions to provide the corresponding phosphoroselenoates and phosphorotelluroates, respectively, in good to excellent yields.
- Choudhary, Rakhee,Singh, Pratibha,Bai, Rekha,Sharma, Mahesh C.,Badsara, Satpal Singh
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p. 9757 - 9765
(2019/12/02)
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- A scalable electrochemical dehydrogenative cross-coupling of P(O)H compounds with RSH/ROH
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A practical, scalable electrochemical dehydrogenative cross-coupling of P(O)H compounds with thiols, phenols and alcohols in both an undivided cell and a continuous-flow setup is disclosed. Its broad substrate scope (>50 examples), good functional-group tolerance and scalability (>10 g) show potential for practical synthesis. A preliminary mechanistic study suggests that the phosphorus radicals are involved in the catalytic cycle.
- Li, Yujun,Yang, Qi,Yang, Liquan,Lei, Ning,Zheng, Ke
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supporting information
p. 4981 - 4984
(2019/05/21)
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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; 0074-0076
(2018/12/01)
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- Dimethyl sulfoxide as a mild oxidant in S-P(O) bond construction: Simple and metal-free approaches to phosphinothioates
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In the presence of dimethyl sulfoxide (DMSO) as a mild oxidant and reaction medium, a simple and efficient protocol has been developed for the preparation of phosphinothioates via oxidative dehydrogenative phosphorylation of thiols with P(O)H compounds. Additionally, a DMSO-mediated oxidative phosphorylation of disulfides is also demonstrated. Notably, these transformations occur efficiently without the help of any transition metal or additive. These reactions are easy to conduct and can be scaled-up, and various phosphinothioates are readily obtained in moderate to excellent yields with excellent chemoselectivity and good functional-group tolerance.
- Sun, Jian-Guo,Weng, Wei-Zhi,Li, Ping,Zhang, Bo
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supporting information
p. 1128 - 1133
(2017/08/18)
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- NHC-Catalyzed Metathesis and Phosphorylation Reactions of Disulfides: Development and Mechanistic Insights
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The development of efficient methods for the metathesis and phosphorylation reactions of disulfide compounds is of widespread interest due to their important synthetic utility in polymer, biological, medicinal and agricultural chemistry. Herein, we demonstrate the use of N-heterocyclic carbenes (NHCs) as versatile organocatalysts to promote these challenging reactions under mild conditions. This metal- and oxidant-free protocol is operationally simple with very short reaction times. The interplay between the nucleophilicity and basicity of NHCs in these reactions were also elucidated by NMR studies and high-level ab initio calculations.
- Crocker, Reece D.,Hussein, Mohanad A.,Ho, Junming,Nguyen, Thanh V.
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supporting information
p. 6259 - 6263
(2017/05/12)
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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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- Photoinduced Coupling Reaction of Diphenyl(2,4,6-trimethylbenzoyl)phosphine Oxide with Interelement Compounds: Application to the Synthesis of Thio- or Selenophosphinates
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Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TMDPO) is a radical initiator widely used in the field of macromolecular chemistry, but not often applied in synthetic organic chemistry. We have focused on the use of TMDPO as a phosphorus source in reactions with different E - E compounds, where E - E represents a heteroatom-heteroatom bond, under photoirradiation. Interestingly, the cross-coupling reaction between TMDPO and disulfides or diselenides successfully affords thio- or selenophosphinates and thio- or selenoesters, respectively. The synthesis of series of thio- and selenophosphinates by this photoinduced cross-coupling reaction is demonstrated.
- Sato, Yuki,Kawaguchi, Shin-Ichi,Nomoto, Akihiro,Ogawa, Akiya
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p. 3558 - 3567
(2017/08/16)
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- Metal- and oxidant-free S-P(O) bond construction: Via direct coupling of P(O)H with sulfinic acids
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We have developed a simple and convenient method for S-P(O) bond formation between R2P(O)H and sulfinic acids under metal-, oxidant-, and halogen-free conditions. The current method is compatible with a broad range of substituents on various substrates including halogens and heterocyclic moieties. The synthetic potential of this method was further highlighted by the expeditious synthesis of optically active P-chiral phosphorothioates via stereospecific coupling.
- Moon, Youngtaek,Moon, Yonghoon,Choi, Hangyeol,Hong, Sungwoo
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p. 1005 - 1013
(2017/08/14)
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- Synthesis of Unsymmetrical Tertiary Phosphine Oxides via Sequential Substitution Reaction of Phosphonic Acid Dithioesters with Grignard Reagents
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A facile synthetic method for unsymmetrical tertiary phosphine oxides is reported. Sequential treatment of phosphonodithioic acid S,S-di(p-tolyl) esters with two Grignard reagents enabled the stepwise introduction of different carbon substituents on the phosphorus atom. The chemical stability of dithioesters and monosubstituted thioesters has enhanced the utility of this method, rendering a wide range of organophosphorus compounds easily available.
- Nishiyama, Yoshitake,Hazama, Yuki,Yoshida, Suguru,Hosoya, Takamitsu
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p. 3899 - 3902
(2017/07/26)
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- Acid/Phosphide-Induced Radical Route to Alkyl and Alkenyl Sulfides and Phosphonothioates from Sodium Arylsulfinates in Water
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A newly developed aqueous system with acid and phosphide was introduced in which odorless and stable sodium arylsulfinates can in situ generate arylsulfenyl radicals. These radicals have high reactivity to react with alkynes, alkenes, and H-phosphine oxides for the synthesis of alkyl and alkenyl sulfides and phosphonothioates. The control experiments and quantum calculations are also performed to gain insights into the generation mechanism of arylsulfenyl radicals. Notably, the chemistry is free of thiol odors, organic solvents, and metals.
- Lin, Ya-Mei,Lu, Guo-Ping,Wang, Gui-Xiang,Yi, Wen-Bin
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p. 382 - 389
(2017/04/26)
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- Metal- and base-free reductive coupling reaction of P(O)-H with aryl/alkyl sulfonyl chlorides: a novel protocol for the construction of P-S-C bonds
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Novel and efficient synthesis of S-aryl/alkyl phosphinothioates from P(O)-H and aryl/alkyl sulfonyl chlorides under metal- and base-free conditions is described. This reaction provides an alternative strategy for the construction of P-S-C bonds in moderate to excellent yields. Moreover, this method can be readily applied to gram-scale preparation.
- Wang, Dungai,Zhao, Jinlong,Xu, Weigang,Shao, Changwei,Shi, Zheng,Li, Liang,Zhang, Xinghua
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supporting information
p. 545 - 549
(2017/01/25)
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- Synthesis of P(O)-S organophosphorus compounds by dehydrogenative coupling reaction of P(O)H compounds with aryl thiols in the presence of base and air
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The synthesis method of P(O)-S organophosphorus compounds by dehydrogenative coupling reaction of P(O)H compounds and aryl thiols was developed. The reaction was carried in the presence of a base and air, and exhibited good characters such as metal-free,
- He, Wei,Hou, Xiao,Li, Xinjin,Song, Liang,Yu, Qing,Wang, Zhongwei
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p. 3133 - 3138
(2017/05/08)
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- Preparation method of thiophosphate compounds
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The invention provides a preparation method of thiophosphate compounds. The method comprises the following step: enabling P (O)-H compounds to react with a compound containing a mercapto functional group in an organic solvent in presence of inorganic base so as to obtain so as to obtain the thiophosphate compounds. According to the preparation method, the P (O)-H compounds are taken as initial raw materials, and a dehydrogenation coupling reaction is carried out in presence of the inorganic base under the conditions of metal-free catalysis and room temperature, so that high-yield thiophosphate or organic phosphate is synthesized; furthermore, the method has good applicability for alkyl phosphite or aryl phosphine oxide which has different substituent groups, and thiophenol. The synthetic route provided by the invention is simple in raw materials, mild in reaction conditions, short in reaction time, high in yield and less in by-products, is beneficial to post-synthesis of thiophosphate medicines having biological activity, reduces metal residue and toxic effects, and provides more directions and choices for the related applications in the aspects of medicines, pesticide and bioactive molecules.
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Paragraph 0140-0146
(2017/08/30)
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- Metal-free electrophilic phosphination of electron-rich arenes, arenols and aromatic thiols with diarylphosphine oxides
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A new protocol for achieving the phosphination of arenes, arenols and thiols has been disclosed. This chemistry, in which diaryl(((trifluoromethyl)sulfonyl)oxy)phosphines as a kind of electrophilic phosphination reagents are in situ generated from diarylp
- Yuan, Tao,Huang, Shenlin,Cai, Chun,Lu, Guo-Ping
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- Catalyst- and oxidant-free coupling of disulfides with H-phosphine oxide: construction of P–S bond leading to thiophosphinates
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An efficient protocol for the synthesis of thiophosphinates is presented, involving direct coupling of P–S bond between disulfides and H-phosphine oxide in moderate to good yields with good functional group compatibility. This procedure shows some advanta
- Xia, Minfang,Cheng, Jiang
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supporting information
p. 4702 - 4704
(2016/10/03)
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- Metal-Free Visible-Light-Mediated Oxidative Cross-Coupling of Thiols with P(O)H Compounds Using Air as the Oxidant
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Visible light along with 5 mol % of rose bengal catalyzes the direct S-P(O) coupling between thiols and P(O)H compounds in the presence of air as the green oxidant. The protocol is operationally simple and amenable to gram-scale synthesis. A variety of S-
- Sun, Jian-Guo,Yang, Hua,Li, Ping,Zhang, Bo
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supporting information
p. 5114 - 5117
(2016/10/14)
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- Direct synthesis of thiophosphates by reaction of diphenylphosphine oxide with sulfonyl chlorides
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A new method for the synthesis of thiophosphates by reductive coupling reaction of diphenylphosphine oxide and sulfonyl chlorides has been developed. The reaction is metal-free and needs no additives, affording various aryl and alkyl substituted thiophosphates in good to excellent yields under mild conditions.
- He, Wei,Wang, Zhiming,Li, Xinjin,Yu, Qing,Wang, Zhongwei
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supporting information
p. 7594 - 7598
(2016/11/11)
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- Method for preparing S-aryl or alkyl thiophosphonate compound
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The invention discloses a method for preparing an S-aryl or alkyl thiophosphonate compound. According to the method, sulfonyl chloride and diphenyl phosphine oxide serve as raw materials, and corresponding S-aryl or alkyl thiophosphonate can be produced through coupling in air at a relatively low temperature without alkalifying. According to the method, synthesis procedures are not involved in intractable substances such as accelerants and metal catalysts, the method is easy and feasible, and the conditions are mild. The synthetic product of the method can be applied to numerous fields of medicines, pesticides, organic synthesis and the like and is an organic synthesized intermediate with excellent performance.
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Paragraph 0016; 0017; 0018; 0019; 0020; 0071; 0072-0102
(2017/07/20)
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- Chloroform-based Atherton-Todd-type reactions of alcohols and thiols with secondary phosphine oxides generating phosphinothioates and phosphinates
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Chloroform-based Atherton-Todd-type reactions of alcohols and thiols with secondary phosphine oxides, generating phosphinothioates and phosphinates, respectively, are described. Various valuable phosphinothioates and phosphinates including those with functional groups are readily prepared under mild reaction conditions.
- Li, Shan,Chen, Tieqiao,Saga, Yuta,Han, Li-Biao
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p. 71544 - 71546
(2015/09/08)
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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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- Oxidative hydrolysis of phosphorus(V) esters of thiols by peroxymonosulfate ion. Reactions of peroxymonosulfate ion with phosphorus(V) esters of thiols
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Peroxymonosulfate ion, HSO5-, as Oxone, readily converts phosphorus(V) esters of thiols into the phosphorus(V) and sulfonic acids. The esters were Ph2PO·SC6H4R(p) with R=MeO (1a), Me (1b), H (1c), Cl (1d) and NO2 (1e), (EtO)2PO·SPh (2), Ph2OI·SEt (3) and PhPO(OEt)SEt (4). Reactions are first order in each reactant and second-order rate constants, k2, for 1a-e fit the Hammett equation with ρ=-0.46. The rate constants increase markedly with increasing water content of H2O-MeCN, the activation enthalpies are low and the entropies are negative. Despite the low value of -ρ, these esters are much less reactive than thiol ethers, but the rate constants of reactions of these compounds and acyl thiols qualitatively follow the ionization potentials of the ethers and the esters.
- Blasko, Andrei,Bunton, Clifford A.,Kumar, Anurag
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p. 427 - 434
(2007/10/03)
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