- 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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- 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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- 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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- 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 0088-0092
(2020/09/12)
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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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- 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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- CDI-promoted direct esterification of P(O)-OH compounds with phenols
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A novel and efficient N,N′-carbonyl diimidazole-catalyzed protocol for the direct esterification of P(O)-OH compounds using phenols as efficient esterification reagents is illustrated. It is a simple way to synthesis a broad spectrum of functionalized O-aryl phosphinates, phosphonates, and phosphates from basic starting materials with moderate to excellent yields.
- Xiong, Biquan,Hu, Chenghong,Li, Haotian,Zhou, Congshan,Zhang, Pangliang,Liu, Yu,Tang, Kewen
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supporting information
p. 2482 - 2486
(2017/05/31)
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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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- 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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- 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 0021; 0022; 0023; 0024; 0025
(2017/07/20)
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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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