- 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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- A phosphoryl radical-initiated Atherton-Todd-type reaction under open air
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A phosphoryl radical-initiated Atherton-Todd-type reaction using air as the radical initiator and CHCl3 as the halogenating reagent for the phosphorylation of alcohols, phenols, and amines has been developed. This novel transformation provides a highly efficient route to important phosphinates, phosphinic amides, and phosphoramidates in up to 99% yield with a broad substrate scope under very mild conditions (48 examples).
- Ou, Yingcong,Huang, Yuanting,He, Zhenlin,Yu, Guodian,Huo, Yanping,Li, Xianwei,Gao, Yang,Chen, Qian
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supporting information
p. 1357 - 1360
(2020/02/11)
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- Highly Efficient and Convenient Access to Phosphinates via CHCl3-Assisted Direct Phosphorylation between R2P(O)H and ROH by Phosphonium Salt Catalysis
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A mild, efficient, convenient and scalable method to synthesize phosphinates via direct phosphorylation between R2P(O)H and ROH was developed. All aromatic substrates completed this transformation with excellent yields (up to 98 %), and preliminary mechanistic studies suggest that a carbene-involving process from CHCl3 to CH2Cl2 facilitates the phosphorylation.
- Jiang, Zhiyu,Wang, Tianli,Yu, Xiaojun,Zhang, Hong-Su,Zhang, Song
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supporting information
(2020/05/25)
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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 0297-0301
(2020/09/12)
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- Base-promoted selective O-phosphorylation of aryl triflates with P(O)-H compounds
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Compared to previous transition metal-catalyzed C-phosphorylation reactions for constructing C–P bonds, in the absence of transition metal catalysts and ligands, a direct O-phosphorylation of aryl triflates selectively occurred with P(O)-H compounds in the presence of a base via the construction of O–P bonds. This transformation proceeds under simple and mild conditions, and provides a new method for the preparation of valuable organophosphoryl compounds from readily available P(O)-H compounds and triflates.
- Wang, Mingyue,Yang, Jia,Wang, Shuai,Zhong, Hong
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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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- Ph3P-mediated highly selective C(α)-P coupling of quinone monoacetals with R2P(O)H: Convenient and practical synthesis of: Ortho -phosphinyl phenols
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A highly selective Ph3P-mediated C(α)-P coupling reaction of quinone monoacetals with secondary phosphine oxides is developed to provide an effective method for the synthesis of a wide array of ortho-phosphinylphenols in good to excellent yields. This protocol can be adopted for scale-up synthesis directly from cheap and abundant phenols, and the products can be easily obtained in high yields by simple filtration without the use of organic extraction or chromatography.
- Shen, Ruwei,Zhang, Ming,Xiao, Jing,Dong, Chao,Han, Li-Biao
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p. 5111 - 5116
(2018/11/24)
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- DCC-assisted direct esterification of phosphinic and phosphoric acids with O-nucleophiles
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A novel and efficient dicyclohexylcarbodiimide-promoted protocol for the selective and controllable esterification of P(O)OH compounds using O-nucleophiles (alcohols and phenols) as efficient esterification reagents is described. This method features a high efficiency and good functional-group tolerance, meaning a simple way to synthesize a broad spectrum of phosphinic and phosphoric acid esters from basic starting materials with moderate to excellent yields.
- Xiong, Biquan,Wang, Gang,Zhou, Congshan,Liu, Yu,Li, Jiandong,Zhang, Pangliang,Tang, Kewen
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supporting information
p. 239 - 244
(2017/11/20)
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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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- Method for preparing organophosphate compound through efficient esterification of P(O)-OH-containing compound and phenol
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The invention provides a method for preparing an organophosphate compound through efficient esterification of a P(O)-OH-containing compound and phenol. The method realizes efficient and highly selective synthesis of organophosphate derivatives containing
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Paragraph 0022
(2017/09/01)
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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 phosphinic acid ester/phosphorous acid ester/phosphoric acid ester from P(O)-OH compound and aryl boronic acid
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The invention provides a method for high-selectivity synthesis of phosphinic acid ester/phosphorous acid ester/phosphoric acid ester derivatives containing different substituted functional groups; a metal salt is used as a catalyst, a P(O)-OH-containing compound and aryl boronic acid are used as reactants, and an alkali, an additive and an organic solvent are added into the reaction system. The method has the advantages that the catalyst is cheap and easy to obtain; the reaction conditions are mild, and the method is safe and reliable; the selectivity of the obtained target product is close to 100%, and the yield is as high as 90% or more. The method solves the deficiency that traditional synthetic phosphinic acid ester/phosphorous acid ester/phosphoric acid ester compounds have poor reaction selectivity, complex reaction steps and low yield and need to use reagents harmful to the environment, and has a good prospect in industrial application. The invention also provides the corresponding phosphinic acid ester/phosphorous acid ester/phosphoric acid ester derivatives correspondingly containing different substituted functional groups.
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Paragraph 0028; 0029
(2016/10/10)
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- Copper-catalyzed direct esterification of P(O)-OH compounds with phenols
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A novel copper-catalyzed method for the direct esterification of P(O)-OH compounds using phenols as efficient esterification reagents is illustrated. It is a simple way to generate a broad spectrum of functionalized O-aryl phosphinates, phosphonates, and phosphates from basic starting materials with moderate to excellent yields.
- Xiong, Biquan,Zeng, Kui,Zhang, Shanshan,Zhou, Yongbo,Au, Chak-Tong,Yin, Shuang-Feng
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supporting information
p. 9293 - 9298
(2015/11/27)
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- Direct aerobic oxidative esterification and arylation of P(O)-OH compounds with alcohols and diaryliodonium triflates
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Copper-catalyzed aerobic oxidative esterification of P(O)-OH compounds is achieved using alcohols as efficient esterification reagents, giving the expected products with good to moderate yields. Furthermore, it is shown that the arylation of P(O)-OH compounds proceeds efficiently to produce the corresponding products via the treatment of diaryliodonium triflates under mild reaction conditions. It is a simple way to produce a broad spectrum of functionalized phosphinates, phosphonates, and phosphates from basic starting materials with good to excellent yields. The protocol is convenient for practical application. A plausible mechanism has been proposed for the reaction.
- Xiong, Biquan,Feng, Xiaofeng,Zhu, Longzhi,Chen, Tieqiao,Zhou, Yongbo,Au, Chak-Tong,Yin, Shuang-Feng
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p. 537 - 543
(2015/04/14)
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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-promoted oxidative-fluorination of arylphosphine under mild conditions
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An efficient method for the synthesis of phosphoric fluoride via oxidative coupling between hydrophosphine oxide and NaF is reported. DDQ serves as the oxidizing reagent as well as the hydrogen acceptor. The process involves a Cu(ii) catalysis and exhibits great functional group tolerance under mild reaction conditions. the Partner Organisations 2014.
- Liu, Na,Mao, Liu-Liang,Yang, Bin,Yang, Shang-Dong
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supporting information
p. 10879 - 10882
(2014/10/15)
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- Metal-catalyzed phosphinyl ester forming reaction of alcohols and phenols with diphosphine disulfides and a dioxide
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Transition metal complexes catalyzed the dialkylphosphinothioation reaction of alcohols and phenols with tetraalkyldiphosphine disulfides in high yields. Phenols were reacted in the presence of RhH(PPh3)4 and 1,2-bis(dimethylphosphino)ethane under THF reflux, and alcohols with Pd(OAc)2 and 1,2-bis(diphenylphosphino)benzene under chlorobenzene reflux. Primary alcohols reacted faster than secondary alcohols under these conditions, and protected tyrosine and serine were phosphinothioated with minimal racemization. Tetraphenyldiphosphine dioxide also underwent the P-O bond formation reaction.
- Arisawa, Mieko,Yamaguchi, Masahiko
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experimental part
p. 4840 - 4842
(2010/10/02)
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- Synthesis, resolution and applications of 3,3′-bis(RO)-MeO-BIPHEP derivatives
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A series of optically pure 3,3′-bis(RO)-MeO-BIPHEP derivatives are prepared and used in palladium catalyzed asymmetric transformations. The phosphine oxide of (±)-5 is prepared in four steps from p-methoxyphenol and resolved using the novel resolving reag
- Gorobets, Evgueni,Sun, Guang-Ri,Wheatley, Bronwen M.M.,Parvez, Masood,Keay, Brian A.
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p. 3597 - 3601
(2007/10/03)
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- A NOVEL SUBSTITUENT EFFECT ON 31P NMR CHEMICAL SHIFTS IN THE ARYL DIPHENYLPHOSPHINATE SERIES
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The 31P NMR chemical shifts of a series of meta- and para-substituted phenyl diphenylphosphinates, Ph2P(O)OC6H4-X, have been determined.The δ 31P values exhibit an increasing downfield trend as the electron-withdrawing properties of the substituent X become greater and a reasonable correlation between δ 31P and Hammett-Taft substituent constants is obtained.This trend is opposite to that exhibited in several families of compounds of the type ArP(O)Y2, where δ 31P values show an increasing upfield trend as the electron-withdrawing ability of the substituent in Ar is increased.The results are explained by proposing varying degrees of d-orbital occupancy in the phosphorous-oxygen bonds (P-OAr and P=O) in the series of compounds as a factor influencing 31P chemical shifts.
- Hoz, S.,Dunn, E. J.,Buncel, E.,Bannard, R. A. B.,Purdon, J. G.
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p. 321 - 326
(2007/10/02)
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