- Proline/pipecolinic acid-promoted copper-catalyzed P-arylation
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We have developed a convenient and efficient approach for P-arylation of organophosphorus compounds containing P-H. Using commercially available and inexpensive proline and pipecolinic acid as the ligands greatly improved the efficiency of the coupling reactions, so the method can provide an entry to arylphosphonates, arylphosphinates and arylphosphine oxides.
- Huang, Cheng,Tang, Xu,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
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- Solubilities of diphenylphosphinic acid in selected solvents
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Diphenylphosphinic acid (DPPA) was synthesized and characterized by infrared spectroscopy (IR), nuclear magnetic resonance (1H NMR), mass spectroscopy (MS), and elemental analysis. The melting point and the enthalpy of fusion of DPPA were measured by a differential scanning calorimeter (DSC), and the thermal stability of DPPA was measured by thermogravimetric analysis (TGA). The solubility data of DPPA in nine solvents were measured and correlated with an empirical equation. The estimated uncertainty of all the solubility values based on error analysis and repeated observations was within 2.0 %.
- Zhang, Gai-Qing,Wang, Li-Sheng,Fan, Rui-Lan,Shao, Xian-Zhao,Wang, Xiao-Fang
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- A 31P-SNP study of the photolysis of (2,4,6-trimethylbenzoyl)diphenylphosphine oxide in micelles of different sizes
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31P stimulated nuclear polarization spectra and their dependence on time after photolysis of (2,4,6-trimethylbenzoyl)diphenylphosphine oxide in micellar solution of sodium octyl- (SOS) and dodecylsulfate (SDS) are investigated and discussed in terms of the numerical solution of the stochastic Liouville equation for a microreactor model.The decay of the geminate radical pair is found to be about 2.5 times slower in SDS than in the SOS micelles due to a larger re-encounter rate in the latter one.Simulation of the experimental results further suggests J0= ca. -1.6*1010 rad/s for the exchange interaction at contact distance, and an increasing micellar size with increasing radical size.
- Ananchenko, G. S.,Bagryanskaya, E. G.,Tarasov, V. F.,Sagdeev, R. Z.,Paul, H.
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- Photoreaction of anthracenyl phosphine oxides: Usual reversible photo- and heat-induced emission switching, and unusual oxidative P&C bond cleavage
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Anthracenyl(diphenyl)phosphine oxide and dianthracenylphenylphosphine oxide as photoactive compounds have been synthesized. Anthracenyl group of these compounds indicate the multi-functional roles such as an emission component, a photodimerization component, and a leaving group. When the light irradiation was performed under an oxygen atmosphere, photo-oxidative P&C bond cleavage to leave the antharacenyl group was observed. Moreover, phosphonyl radical was produced and then P&P bond formation to form diphosphane was observed.
- Katagiri, Kosuke,Yamamoto, Yukina,Takahata, Yuui,Kishibe,Fujimoto
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- Synthesis, Structure, and Coordination Chemistry of Phosphine-Functionalized Imidazole/Imidazolium Salts and Cleavage of a C-P Bond in an NHC-Phosphenium Salt using a Pd(0) Precursor
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A simple method involving metal-halogen exchange reaction(s) to prepare various phosphine-functionalized imidazole/imidazolium salts and their coordination chemistry with different metal precursors has been described. Interestingly, the reaction of 1,3-dimethyl-2-(diphenylphosphino)-4-iodoimidazolium iodide (6) with Pd2(dba)3 in the presence of triphenylphosphine affords a Pd(II)-NHC complex which involves the cleavage of a C-P bond presumably occurring via oxidative addition of Pd(0) to a C-I bond to afford an in situ generated Pd(II) species, which subsequently reacts with another 1 equiv of 6 through the phosphine center to form an adduct followed by a dephosphinylation reaction. (Chemical Equation Presented).
- Karthik, Vedhagiri,Gupta, Vivek,Anantharaman, Ganapathi
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- Establishment of a new molecular model for mercury determination verified by single crystal X-ray diffraction, spectroscopic analysis and biological potentials
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A wide variety of molecular probes have been developed for real-time analysis, but most of organic fluorophores possess small Stokes shifts and self-absorption or inner filter effect that could not be avoided. In this study, a new dicyanoisophorone-based derivative (E)-O-(4-(2-(3-(dicyanomethylene)-5,5-dimethylcyclohex-1-en-1-yl)vinyl)phenyl)diphenylphosphinothioate (λex = 405 nm, λem = 551 nm, denoted as ICM-S) with strong push-pull electron effect has been afforded and it exhibits red shift for absorption from 407 nm to 426 nm with distinct color change from pale yellow to deep yellow upon exposure to Hg2+. Moreover, an easily distinguishable fluorescence color change follows the route from green, yellow to red in the presence of Hg2+ over the range of 0?90 μmol/L (detection limit = 137 nmol/L) can be observed by the naked eye under a UV lamp irradiation. Chlorodiphenylphosphine and sublimed-sulfur are incorporated as responsive sites and P-O bond has been cleaved upon the addition of mercury ions. During the recognition process, such dicyanoisophorone dye (ICM-S) has been evolved to 2-(3-(4-hydroxystyryl)-5,5-dimethylcyclohex-2-enylidene) malononitrile (ICM?OH). Clear evidences in the chemical processes can be identified via single crystal X-ray diffraction, spectroscopic analysis, photophysical studies and titration experiments. With the aim of exploring its potential in biological systems, its in vitro responses to Hg2+ have been evaluated in 293 T cells and the effectiveness in zebrafish model has also been verified.
- Gu, Jiapei,Zhang, Feifan,Zheng, Ziman,Li, Xiangqian,Deng, Runxuan,Zhou, Zhan,Ma, Lufang,Liu, Wanqiang,Wang, Qianming
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- The Catalytic Role of Iodide Ion/Iodine Couple in the Photo-Reduction of 10-Methylacridinium Ion with Diphenylphosphine Oxide
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Photo-redox between diphenylphosphine oxide and 10-methylacridinium iodide with visible light in aqueous acetonitrile under argon atmosphere is initiated by single electron transfer from the phosphorus compound to the acridinium salt in the potoexcited state giving diphenylphosphinic acid and 10-methylacridan as the final products.Iodide ion/iodine couple plays a crucial role for transferring an electron in this reaction.
- Yasui, Shinro,Shioji, Kosei,Ohno, Atsuyoshi,Yoshihara, Masakuni
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- Direct synthesis of α-hydroxyketone phosphates from terminal alkynes and H-phosphine oxides in the presence of PhI(OAc)2and H2O
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A simple and highly efficient one-pot method for the construction of α-hydroxyketone phosphates from terminal alkynes and H-phosphine oxides has been developed in the presence of PhI(OAc)2and H2O. The present protocol provides an attractive approach to α-hydroxyketone phosphates in good to high yields, with the advantages of operation simplicity, the use of commercially available materials, broad substrate scope, high atom efficiency and good tolerance to scale-up synthesis.
- Hu, Dong-Yan,Li, Meng-Shun,Zhong, Wen-Wu,Ji, Jian-Xin,Zhu, Jin,Wei, Wei,Zhang, Qiang,Cheng, Ming
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- Dramatic effect of the metal cation in dealkylation reactions of phosphinic esters promoted by complexes of polyether ligands with metal iodides
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Metal ion electrophilic catalysis has been revealed in dealkylation reactions of phosphinic esters 1-4 promoted by complexes of polyether ligands 5-7 with metal iodides MIn (Mn+ = Li+, Na+, K+, Rb+, Ca2+, Sr2+, Ba2+) in low polarity solvents (chlorobenzene, 1,2-dichlorobenzene, and toluene) at 60 °C. The catalytic effect increases with increasing the Lewis acid character of the cation, in the order Rb+ + + + and Ba2+ 2+ 2+. The results are interpreted in terms of a transition state where the complexed cation (Mn+ ? Lig) assists the departure of the leaving group Ph2P(O)O- and, at the same time, favors the attack at carbon of the nucleophile I- ( push-pull mechanism). The rate sequence found for 1-4 (Me > Et ? i-Pr and t-Bu) shows that this reaction can be utilized for the selective dealkylation of these substrates.
- Albanese,Landini,Maia
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- Phosphinite-phosphine oxide isomerization of diphenylphosphinite derivatives of 1,4:3,6-dianhydro-D-mannitol
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Phosphorylation of 1,4:3,6-dianhydro-D-mannitol with diphenylphosphinous chloride provided a bisphosphinite derivative that, unlike what is observed in the phosphorylation with phosphorous chlorides and amides, undergoes fast phosphinite-phosphine oxide isomerization. The monophosphinite derivative, in addition, is strongly dephosphorylated. The effect of the solvents and amines (HCl acceptors) on the phosphinite-phosphine oxide isomerization is studied.
- Kurochkina,Soboleva,Vasyanina,Grachev,Nifant'ev
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- Addition of diphenylphosphinoyl azide to [60]fullerene
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The reaction of [60]fullerene with diphenylphosphinoyl azide in toluene or in o-dichlorobenzene in the presence of traces of water affords 2-[N-(diphenylphosphoryl)amino]-1-hydroxy [60]fullerene. This reaction in THF gives a mixture of (N-diphenylphosphoryl)[60]fullereno[1,2-6]aziridine and a product of partial hydrolysis of the bisadduct of phosphorylated azide and fullerene.
- Romanova,Sinyashin,Yusupova,Kovalenko,Efremov,Badeev,Vandyukova,Arakelyan
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- Insertion of phosphinidene complexes into the P-H bond of secondary phosphine oxides: A new version of the phospha-Wittig synthesis of P=C double bonds
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Terminal phosphinidene complexes [RP-W(CO)5], as generated at 60 °C in the presence of copper chloride from the appropriate 7-phosphanorbornadiene complexes, react with secondary phosphine oxides Ar2P(O)H to give the insertion products into the P-H bonds. After metalation with NaH, these products react with aldehydes to give the corresponding phosphaalkenes which are trapped by dimethylbutadiene.
- Hao, Yanwei,Wu, Di,Tian, Rongqiang,Duan, Zheng,Mathey, Fran?ois
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- Raman Fiber Photometry for Understanding Mitochondrial Superoxide Burst and Extracellular Calcium Ion Influx upon Acute Hypoxia in the Brain of Freely Moving Animals
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Developing a novel tool capable of real-time monitoring and simultaneous quantitation of multiple molecules in mitochondria across the whole brain of freely moving animals is the key bottleneck for understanding the physiological and pathological roles that mitochondria play in the brain events. Here we built a Raman fiber photometry, and created a highly selective non-metallic Raman probe based on the triple-recognition strategies of chemical reaction, charge transfer, and characteristic fingerprint peaks, for tracking and simultaneous quantitation of mitochondrial O2.?, Ca2+ and pH at the same location in six brain regions of free-moving animal upon hypoxia. It was found that mitochondrial O2.?, Ca2+ and pH changed from superficial to deep brain regions upon hypoxia. It was discovered that hypoxia-induced mitochondrial O2.? burst was regulated by ASIC1a, leading to mitochondrial Ca2+ overload and acidification. Furthermore, we found the overload of mitochondrial Ca2+ was mostly attributed to the influx of extracellular Ca2+.
- Chen, Jinquan,Feng, Enduo,Liu, Yangyi,Liu, Yuandong,Liu, Zhichao,Mei, Yuxiao,Tian, Yang,Zhang, Sanjun,Zhang, Zhonghui,Zheng, Tingting
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supporting information
(2022/03/03)
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- Potassium tert -Butoxide Mediated Reductive C-P Cross-Coupling of Arylvinyl Sulfides through C-S Bond Cleavage
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A transition-metal-free t -BuOK-mediated reductive C-P cross-coupling reaction of arylvinyl sulfides with diarylphosphine oxides through C-S bond cleavage has been developed. This protocol not only permits the synthesis of diaryl(2-arylethyl)phosphine oxides, but also achieves an unprecedented construction of a C-P bond through C-S bond cleavage and reduction of a C-C double bond in one pot.
- Feng, Jie,Zhang, Qiaoling,Li, Fuhai,Yang, Lu,Kuchukulla, Ratnakar Reddy,Zeng, Qingle
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p. 224 - 228
(2020/10/30)
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- Temporary (P=O) directing group enabled carbazoleorthoarylationviapalladium catalysis
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A palladium-catalyzed, temporary P(O) directing group assisted C-H bond arylation of carbazoles was achieved. The release of the directing group occurs spontaneously in the reaction and the mechanistic studies indicate that acid is essential for N-P bond cleavage.
- Qi, Zhi-Chao,Lou, Qin-Xin,Niu, Yuan,Yang, Shang-Dong
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p. 2021 - 2024
(2021/03/01)
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- Selective hydrolysis of phosphorus(v) compounds to form organophosphorus monoacids
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An azide and transition metal-free method for the synthesis of elusive phosphonic, phosphinic, and phosphoric monoacids has been developed. Inert pentavalent P(v)-compounds (phosphonate, phosphinate, and phosphate) are activated by triflate anhydride (Tf2O)/pyridine system to form a highly reactive phosphoryl pyridinium intermediate that undergoes nucleophilic substitution with H2O to selectively deprotect one alkoxy group and form organophosphorus monoacids.
- Ash, Jeffrey,Cordero, Paula,Huang, Hai,Kang, Jun Yong
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p. 6007 - 6014
(2021/07/21)
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- Hydrolysis and alcoholysis of phosphinates and phosphonates
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Phosphinic and phosphonic acids useful intermediates and biologically active compounds may be prepared from their esters: phosphinates and phosphonates, respectively, by acid-catalyzed hydrolysis either on conventional heating or on MW irradiation. The transesterification of alkyl phosphinates took place only in the presence of suitable ionic liquids as the catalysts. In the cases of phenylphosphonates, depending on the nature of the ionic liquid, the formation of the ester was accompanied by the fission of the C–O bond.
- Harsági, Nikoletta,Keglevich, Gy?rgy,Sz?ll?si, Betti,Varga, Petra Regina
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- Synthesis and structural characterization of phosphinate coordination polymers with tin(IV) and copper(II)
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In this work, we report the synthesis and X–ray characterization of diphenylphosphinic acid (L) (redetermination at 100 K), and its two polymeric phosphinate complexes; [(C6H5)2P(O)OSn(C6H5)3]n (C1) and [Cu(O2PPh2)2]n (C2), resulted from the bidentate coordinatioan of L. Sn(IV) centers in C1 are five-coordinate in a distorted trigonal bipyramidal geometry. One dimensional coordination chains of C2 are made by double-bridging ligands between the copper atoms, surrounded with four P–O in a square planar polyhedron. Structural characterization of the complexes revealed that M ? O bonds are responsible for the assembly of the primary structural motifs in both the complexes while C–H … π and H?H interactions are effective in organizing these molecules into extended 3D architectures. The quantitative mapping of interactions was also analyzed using Hirshfeld surface analysis. With respect to the 31PNMR spectra, there are probably fast transformations in the solution and different types of coordinated and dissociated species are in balance, consistent with the optimized structures in the solvent and gas phases.
- Gholivand, Khodayar,Fallah, Nasrin,Ebrahimi Valmoozi, Ali Asghar,Gholami, Akram,Dusek, Michal,Eigner, Vaclav,Pooyan, Mahsa,Mohammadpanah, Fahimeh
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- Controllable phosphorylation of thioesters: Selective synthesis of aryl and benzyl phosphoryl compounds
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The controllable phosphorylations of thioesters were developed. When the reaction was catalyzed by a palladium catalyst, aryl or alkenyl phosphoryl compounds were generated through decarbonylative coupling, while the benzyl phosphoryl compounds were produced through deoxygenative coupling when the reaction was carried out in the presence of only a base.
- Xu, Kaiqiang,Liu, Long,Li, Zhaohui,Huang, Tianzeng,Xiang, Kang,Chen, Tieqiao
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supporting information
p. 14653 - 14663
(2020/12/29)
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- Copper-Catalyzed Oxidative C(sp3)?H/N?H Cross-Coupling of Hydrocarbons with P(O)?NH Compounds: the Accelerating Effect Induced by Carboxylic Acid Coproduct
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An chelation-assisted oxidative C(sp3)?H/N?H cross coupling of hydrocarbons with P(O)?NH compounds using copper acetate as catalyst is described. The results of kinetic experiments, mechanistic studies and DFT calculations demonstrate the importance of acetic acid coproduct as an additive for promoting the formation of intermediate bis((diphenylphosphoryl)(quinolin-8-yl)amino)copper (6), and consequently accelerating the construction of C(sp3)?N bond. The reaction proceeded efficiently with a wide array of hydrocarbons and P(O)?NH compounds, and the rate acceleration induced by the acetic acid coproduct have been repeatedly proven. Furthermore, the efficiency of small-scale reaction could be retained upon gram-scale synthesis in a continuous manner. (Figure presented.).
- Lei, Jian,Yang, Yincai,Peng, Lingteng,Wu, Lesong,Peng, Ping,Qiu, Renhua,Chen, Yi,Au, Chak-Tong,Yin, Shuang-Feng
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p. 1689 - 1696
(2019/03/07)
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- A two-photon fluorescent probe for colorimetric and ratiometric monitoring of mercury in live cells and tissues
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Owing to the extreme toxicity of mercury, methods for its selective and sensitive sensing in solutions, and in live cells and tissues are in great demand. In this study, we developed a naphthalimide-based diphenylphosphinothioyl group-containing fluorescent and colorimetric probe that selectively detects mercury (Hg2+). Upon addition of mercury (Hg2+) to a solution of the probe, both a colorimetric change from colorless to yellow and a fluorescence change from blue to green (under a 365 nm hand-held UV lamp) occur, both of which can be observed using the "naked-eye". Furthermore, the probe possesses the capability of sensing intracellular mercury in both live cells and tissues using dual-emission channels and two-photon microscopy.
- Chen, Liyan,Park, Sang Jun,Wu, Di,Kim, Hwan Myung,Yoon, Juyoung
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supporting information
p. 1766 - 1769
(2019/02/12)
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- Two-Photon Fluorescence Probe for Selective Monitoring of Superoxide in Live Cells and Tissues
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The abnormal location or generation of superoxide radical anion (O2 ?-) are implicated in many diseases, including cancers; thus, development of an efficient method to detect O2 ?- is of great importance. Inspired by the fluorophore-governed selective manner to O2 ?- and peroxynitrite (ONOO-) of previously reported phosphinate-based fluorescence probes, in this contribution, a phosphinothioate-containing probe, TPP, was designed. The probe exhibited easy accessibility through a one-step sequence and good photostability and biocompatibility. Interestingly, TPP showed high specificity and sensitivity to O2 ?- over other reactive oxygen species/nitrogen species including ONOO-. Furthermore, with the assistance of two-photon microscopy, TPP was successfully applied for imaging endogenous O2 ?- in live cells and tissues.
- Chen, Liyan,Cho, Myoung Ki,Wu, Di,Kim, Hwan Myung,Yoon, Juyoung
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- Method for synthesis of organophosphorus compound by photo-induced iodine catalyzed Atherton-Todd reaction
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The invention belongs to the technical field of organic synthesis, discloses a method for synthesis of organophosphorus compound by photo-induced iodine catalyzed Atherton-Todd reaction. The method comprises the following steps: a compound shown as formula II and a nucleophilic reagent are subjected to reaction for 24 hours in a dichloromethane solvent, an oxygen atmosphere, under irradiation condition of room temperature and the action of a halogenated reagent I2, then the organophosphorus compound shown as the formula II is obtained through washing, drying, separating and purifying. According to the the method provided by the invention, compared with traditional Atherton-Todd reaction, no catalysis of metal is needed,no addition of alkali is needed, reaction environment such as metal, high temperature and strong base is replaced, a series of organophosphorus compounds can be synthesized by catalyzing a variety of substrates under the irradiation condition of room temperature, and hasthe advantages of good universality, short reaction time and higher yield.
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Paragraph 0033
(2018/12/14)
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- Chelation-assisted C-N cross-coupling of phosphinamides and aryl boronic acids with copper powder at room temperature
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A protocol for the chelation-assisted C-N cross-coupling of phosphinamides and aryl boronic acids with copper powder under an oxygen atmosphere is reported. This reaction proceeds efficiently to afford fully substituted unsymmetrical N-arylation phosphinamides at room temperature in excellent yields. Diverse unstable functional groups on the benzene ring of aryl boronic acids such as vinyl, formyl, acetyl, sulfonyl, acetylamino, cyano, nitro, and trifluoromethyl can be accommodated.
- Peng, Yao,Lei, Jian,Qiu, Renhua,Peng, Lingteng,Au, Chak-Tong,Yin, Shuang-Feng
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supporting information
p. 4065 - 4070
(2018/06/12)
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- Direct, oxidative halogenation of diaryl- or dialkylphosphine oxides with (dihaloiodo)arenes
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The oxidative halogenation of diaryl- or dialkylphosphine oxides with the hypervalent iodine reagents (difluoroiodo)toluene (p-TolIF2, 1) and (dichloroiodo)benzene (PhICl2, 2) is reported. Phosphoric fluorides could be recovered in 32–75% yield, or they could be trapped with EtOH to give the corresponding phosphinate in typically good yield. Phosphoric chlorides were not readily isolable, and were trapped with alcohol and amine nucleophiles, giving diaryl- or dialkylphos-phinates and phosphinamides in up to 90% yield.
- Eljo, Jasmin,Murphy, Graham K.
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supporting information
p. 2965 - 2969
(2018/06/30)
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- Rhodium(III)-Catalyzed Enantiotopic C?H Activation Enables Access to P-Chiral Cyclic Phosphinamides
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Compounds with stereogenic phosphorus atoms are frequently used as ligands for transition-metal as well as organocatalysts. A direct catalytic enantioselective method for the synthesis of P-chiral compounds from easily accessible diaryl phosphinamides is presented. The use of rhodium(III) complexes equipped with a suitable atropochiral cyclopentadienyl ligand is shown to enable an enantiodetermining C?H activation step. Upon trapping with alkynes, a broad variety of cyclic phosphinamides with a stereogenic phosphorus(V) atom are formed in high yields and enantioselectivities. Moreover, these can be reduced enantiospecifically to P-chiral phosphorus(III) compounds.
- Sun, Yang,Cramer, Nicolai
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supporting information
p. 364 - 367
(2016/12/30)
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- O -Phthalaldehyde catalyzed hydrolysis of organophosphinic amides and other P(O)-NH containing compounds
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Over 50 years ago, Jencks and Gilchrist showed that formaldehyde catalyses the hydrolysis of phosphoramidate through electrophilic activation, induced by covalent attachment to its nitrogen atom. Given our interest in the use of aldehydes as catalysts, this work was revisited to identify a superior catalyst, o-phthalaldehyde, which facilitates hydrolyses of various organophosphorus compounds bearing P(O)-NH subunits under mild conditions. Interestingly, chemoselective hydrolysis of the P(O)-N bonds could be accomplished in the presence of P(O)-OR bonds.
- Li, Bin-Jie,Simard, Ryan D.,Beauchemin, André M.
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p. 8667 - 8670
(2017/08/10)
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- A Direct Catalytic Synthesis of Sodium Diarylphosphinates and Their Corresponding Acids from Sodium Phosphinate
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In this contribution we present the direct conversion of sodium phosphinate (NaH2PO2·H2O) to symmetrical sodium diarylphosphinates and their corresponding acids by using palladium catalysis. This route eliminates the need for chlorinated precursors, such as PCl3and intermediate alkyl- or ammoniumphosphinates.
- Botez, Laurian,de Jong, G. Bas,Slootweg, J. Chris,Deelman, Berth-Jan
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supporting information
p. 434 - 437
(2017/02/05)
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- Tuning the cytotoxicity of ruthenium(ii) para-cymene complexes by mono-substitution at a triphenylphosphine/phenoxydiphenylphosphine ligand
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The new complexes [RuCl2(η6-p-cymene)(κP-Ph2PR)] [R = 4-C6H4OSiMe2tBu, 1; R = 4-C6H4Br, 2; R = OC(O)CHCl2, 3; R = OPh, 4; R = O(2-C6H4SiMe2tBu), 5] and [Ru(C2O4)(η6-p-cymene){κP-Ph2PO(2-C6H4(SiMe2tBu))}], 6, were obtained in 83-98% yield from Ru(ii) arene precursors by three different synthetic strategies. The unprecedented phosphine Ph2P(O(2-C6H4SiMe2tBu)) was synthesized in 86% yield from 2-C6H4Br(OSiMe2tBu) and Ph2PCl, via intramolecular oxygen to carbon 1,3 migration of the silyl group (retro-Brook rearrangement). All the complexes were fully characterized by analytical and spectroscopic methods, and by single crystal X-ray diffraction in the cases of 3, 4, 5 and 6. Complexes 1-6 and the model compounds [RuCl2(η6-p-cymene)(κP-PPh3)] (Ru-PPh3) and [Ru(C2O4)(η6-p-cymene)(κP-PPh3)] (Ru-PPh3-O) underwent slow degradation in chloroform solutions upon air contact; the mixed valence complex [(η6-p-cymene)Ru(μ-Cl)3RuCl2(κP-PPh3)], 7, was isolated from a solution of Ru-PPh3 in CHCl3, and X-ray identified. The antiproliferative activity of 1-6 and Ru-PPh3, Ru-PPh3-O and [RuCl2(η6-p-cymene)(κP-PTA)] (RAPTA-C) was assessed towards the triple-negative breast cancer cell line MDA-MB-231, the ovarian carcinoma cell line A2780 and human skin fibroblasts (HSF). Complexes 1, 2, 5 and 6 displayed IC50 values significantly lower than that of cisplatin, with 2 providing a more potent cytotoxic effect on MDA-MB-231 and A2780 cancer cells compared to the noncancerous cell line (HSF). The stability of all complexes in DMSO/water solution was elucidated by NMR and conductivity measurements, and in particular 35Cl NMR spectroscopy was helpful to check the possible chloride dissociation. The stability studies suggest that the cytotoxic activity in vitro of the compounds is mainly ascribable to Ru(ii) species still bound to the phosphorus ligand.
- Biancalana, Lorenzo,Zacchini, Stefano,Ferri, Nicola,Lupo, Maria Giovanna,Pampaloni, Guido,Marchetti, Fabio
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supporting information
p. 16589 - 16604
(2017/12/15)
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- Copper catalyzed one-pot synthesis of β-ketophosphine oxides from ketones and H-phosphine oxides
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A facile and efficient copper catalyzed one-pot method has been developed for the formation of β-ketophosphine oxides from ketones and H-phosphine oxides under air at room temperature, in which vinylhydrazinedicarboxylate was formed as the key intermediate. Preliminary mechanistic studies indicated that the reaction might involve a radical process and carbonyl oxygen atom of β-ketophosphine oxides came from molecular oxygen.
- Zhang, Zhi-Jie,Yi, Dong,Fu, Qiang,Liang, Wu,Chen, Su-Yuan,Yang, Lu,Du, Feng-Tian,Ji, Jian-Xin,Wei, Wei
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supporting information
p. 2417 - 2420
(2017/06/01)
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- Electrophilic Fluorination of Secondary Phosphine Oxides and Its Application to P-O Bond Construction
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A novel and efficient electrophilic fluorination of secondary phosphine oxides with Selectfluor has been achieved. This transformation provides direct access to phosphoric fluorides in up to 92% yield under mild conditions. In addition, P-O bond construction via a one-pot coupling process of secondary phosphine oxides with water or alcohols in the presence of Selectfluor leads to the formation of phosphinic acids or phosphinates in up to 96% yield.
- Chen, Qian,Zeng, Jiekun,Yan, Xinxing,Huang, Yulin,Wen, Chunxiao,Liu, Xingguo,Zhang, Kun
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p. 10043 - 10048
(2016/11/02)
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- Catalyst-free direct difunctionalization of alkenes with H-phosphine oxides and dioxygen: A facile and green approach to β-hydroxyphosphine oxides
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A simple and catalyst-free method has been developed for the construction of β-hydroxyphosphine oxides through direct difunctionalization of alkenes with H-phosphine oxides and dioxygen under mild conditions. Preliminary mechanistic studies indicated that the hydroxyl oxygen atom of β-hydroxyphosphine oxide originated from the dioxygen and the present reaction might involve a radical process.
- Li, Meng-Shun,Zhang, Qiang,Hu, Dong-Yan,Zhong, Wen-Wu,Cheng, Ming,Ji, Jian-Xin,Wei, Wei
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supporting information
p. 2642 - 2646
(2016/06/01)
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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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p. 7594 - 7598
(2016/11/11)
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- Pd(II)-catalyzed enantioselective synthesis of P-stereogenic phosphinamides via desymmetric C-H arylation
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We present the enantioselective synthesis of P-stereogenic phosphinamides through Pd-catalyzed desymmetric ortho C-H arylation of diarylphosphinamides with boronic esters. The method represents the first example of the synthesis of P-stereogenic phosphorus compounds via the desymmetric C-H functionalization strategy. The reaction proceeded efficiently with a wide array of reaction partners to afford the P-stereogenic phosphinamides in up to 74% yield and 98% ee. The efficiency was further demonstrated by gram scale syntheses. Moreover, the flexible conversion of the P-stereogenic phosphinamides into various types of P-stereogenic phosphorus derivatives was also elaborated. Thus, the protocol provides a novel tool for the efficient and versatile synthesis of P-stereogenic compounds.
- Du, Zhi-Jun,Guan, Jing,Wu, Guo-Jie,Xu, Peng,Gao, Lian-Xun,Han, Fu-She
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supporting information
p. 632 - 635
(2015/01/30)
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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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- The reaction activity of aromatic carbonyl compounds with diphenylphosphine oxide studied by 31P NMR
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A series of α-hydroxyphosphine oxides were prepared by the reactions of diphenylphosphine oxide and aromatic carbonyl compounds and characterized by 1H NMR, 13C NMR, 31P NMR, FT-IR, ESI-MS, and HR-MS spectra. The reaction rates and experimental conditions of aromatic aldehydes and aromatic ketones were obviously different due to the activity of their carbonyls. The different substituents of the aromatic aldehydes affected the reaction rate too, and the quantitative reactivity of their substituent conformed to the Hammett equation. The results were confirmed by 31P NMR spectroscopy.
- Zheng, Jinyun,Feng, Xiangming,Yu, Yujian,Zhen, Xiaomin,Zhao, Yufen
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p. 1080 - 1087
(2013/09/02)
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- Kinetics and reaction mechanism for alkaline hydrolysis of Y-substituted-phenyl diphenylphosphinates
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The second-order rate constants (kOH-) for the reactions of Y-substituted-phenyl diphenylphosphinates (4a-4i) with OH- in H 2O at 25.0 ± 0.1 °C have been measured spectrophotometrically. Comparison of kOH- with kEtO- (the second-order rate constants for the corresponding reactions with E tO- in ethanol) has revealed that EtO- is less reactive than OH- although the former is ca. 3.4 pKa units more basic than the latter, indicating that the reactivity of these nucleophiles is not governed by their basicity alone. The Bronsted-type plot for the reactions of 4a-4i with OH- is linear with βlg = -0.36. The Hammett plot correlated with σ- constants results in a slightly better correlation than that correlated with σo constants but exhibits many scattered points. In contrast, the Yukawa-Tsuno plot for the same reactions exhibits an excellent linear correlation with ρ = 0.95 and r = 0.55. The r value of 0.55 implies that a negative charge develops partially on the O atom of the leaving group. Thus, the reactions of 4a-4i with OH- have been concluded to proceed through a concerted mechanism. Copyright
- Hong, Hyo-Jeong,Lee, Jieun,Bae, Ae Ri,Um, Ik-Hwan
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p. 2001 - 2005
(2013/09/02)
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- Stoichiometry of the reaction of diphenylchlorophosphine with dimethylformamide in the presence of NaI
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Stoichiometric relations of initial compounds and reaction products in the synthesis of N,N-dialkyl-(diphenylphosphinomethylene)iminium are established; the second reaction product is diphenylphosphinic iodide. Bringing triphenylphosphine into the reaction increases the N,N- dialkyl(diphenylphosphinomethylene)-iminium yield approximately twice. One of the reaction intermediates is shown to be iododiphenylphosphine. The reaction can be regarded as disproportionation.
- Morgalyuk,Petrovskii,Lysenko,Nifant'Ev
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experimental part
p. 100 - 105
(2010/05/01)
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- Synthesis of o-(diphenylphosphinoyloxy)anilines by the rhodium-catalyzed reaction of nitroarenes and diphenylphosphine oxide
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A rhodium complex Rh2(OAc)4 catalyzed the reaction of nitrobenzenes and diphenylphosphine oxide HP({double bond, long}O)Ph2 giving o-(diphenylphosphinoyloxy)anilines predominantly, which were accompanied by small amounts of the p-isomers. Nitorobenzenes possessing a bulky o-substituent, particularly o-(t-butyl)nitrobenzenes, underwent the reaction in high yields. The reaction is considered to involve the reductive formation of O-phosphinoyl-N-arylhydroxyamines from nitrobenzenes, and o-phosphinoyloxylation by the rearrangement.
- Arisawa, Mieko,Kuwajima, Manabu,Yamaguchi, Masahiko
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supporting information; experimental part
p. 3116 - 3118
(2010/08/07)
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- Synthesis of new thiazole-2, -4, and -5-yl-(amino)methylphosphonates and phosphinates: Unprecedented cleavage of thiazole-2 derivatives under acidic conditions
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An efficient and reliable synthesis of new thiazole-(amino) methylphosphonic, phosphinic acids, and phosphine oxides is reported. The synthetic protocol is based on nucleophilic addition of phosphorous species to thiazole derived imines. Unexpectedly, it was discovered that heating of thiazole-2-yl-(amino)methylphosphonates and phosphinates with aqueous HCl leads to their decomposition resulting in a rupture of the C-P bond, rejecting of the phosphorus containing fragment and formation of the corresponding secondary N-(thiazole-2-yl-methyl)-alkylamines. Two alternative mechanisms for this cleavage are postulated.
- Olszewski, Tomasz Krzysztof,Boduszek, Bogdan
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experimental part
p. 8661 - 8666
(2011/01/04)
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- Phosphorylation of 2-azabicyclo[2.2.1]hept-5-ene and 2-hydroxy-2- azabicyclo[2.2.1]hept-5-ene systems: Synthesis and mechanistic study
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The endo and exo isomers of (±)-methyl 2-hydroxy-2-azabicyclo[2.2.1] hept-5-ene-3-carboxylates and the in situ-prepared endo and exo isomers of (±)-methyl 2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate were treated with diphenylphosphinic chloride (OPClPh2) and chlorodiphenylphosphine (ClPPh2) to afford the corresponding phosphorylated bicycles. The structure of all these compounds was unequivocally determined by NMR spectroscopy and mass spectrometry, and, based on the results obtained, a mechanistic scheme for the phosphorylation reaction of these adducts to afford the corresponding phosphorylbicycles is proposed.
- Sousa, Carlos A. D.,Vale, M. Luisa C.,Rodriguez-Borges, Jose E.,Garcia-Mera, Xerardo
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experimental part
p. 2546 - 2551
(2011/01/12)
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- Synthesis of nonsymmetrical dialkylamines on the basis of diphenylphosphinic amides
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A facile method for the synthesis of nonsymmetrical dialkylamines (C nH2n+1)2NH (n = 1-12) using the Ph 2P(O) protecting group was developed. The method includes successive transformation of monoalkylamines to primary diphenylphosphinic N-alkylamides Ph2P(O)NHR' (R' = CnH2n+1, n = 1-12) by the Todd-Atherton reaction, phase transfer N-alkylation of these compounds, and hydrolysis of the secondary amides Ph2P(O)NR'R″ thus formed. When the (EtO)2P(O) and Bu2P(O) protecting groups are used, N-alkylation of primary amides is accompanied by the formation of Et-O and P-N bond cleavage products, respectively. A study of the stability of the N-alkylamides R2P(O)NHR' (R = Ph, p-MeC6H4, p-CIC6H4, Bu) under strong alkaline conditions used in the phase transfer N-alkylation showed that an increase in the electron-donating ability of substituents at both the nitrogen atom and the phosphorus atom results in a decrease in the degree of P-N bond cleavage. The primary and secondary diphenylphosphinic amides containing a β-hydroxyethyl group at the nitrogen atom are extremely unstable under the alkaline conditions and are converted quantitatively to the diphenylphosphinic acid salt.
- Bondarenko,Kharlamov,Vendilo
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p. 1872 - 1885
(2011/01/06)
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- Direct conversion of secondary phosphine oxides and h-phosphinates with [Di(acyloxy)iodo]benzenes to phosphinic and phosphonic amides
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The reaction of [di(acyloxy)iodo]- benzene with secondary phosphine oxides or H-phosphinates in the presence of primary or secondary amines allows one to obtain phosphinic or phosphonic acids amides in the one-pot process. We take advantage of the strong acylating system DAIB/R2P(O)H to phosphinylation of amines. However, the reaction mechanism is multipathway and causes yields of phosphinic or phosphonic acids amides to be moderate. When the concentration of amines is low, the intermolecular process plays a main role leading to the formation of carboxylic amides through mixed phosphoric-carboxylic anhydride, and also in the low concentration of amines, tetrahydrofuran effectively competes with the amines in the nucleophilic attack on the acylating intermediates.
- Hubacz, Anna,Makowiec, Slawomir
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body text
p. 81 - 86
(2009/09/25)
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- Efficient synthesis of mono- and diarylphosphinic acids: a microwave-assisted palladium-catalyzed cross-coupling of aryl halides with phosphinate
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A general, efficient method for the microwave-assisted synthesis of mono- and diarylphosphinic acids from anilinium phosphinate and aryl halides, using Pd(0) and Xantphos as a supporting ligand, was developed.
- Kalek, Marcin,Stawinski, Jacek
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experimental part
p. 10406 - 10412
(2010/02/27)
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- N-alkylation of amidothiophosphoryl compounds under phase-transfer catalysis conditions. Synthesis and properties of 1,3,2-thiazaphosphacyclanes
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N (ω-Haloalkyl)amidothiophosphates, N (ω-Haloalkyl) amidothiophosphonates, and N- (ω-Haloalkyl)amidothiophosphinates (Hal = Cl or Br) were obtained in high yields by alkylation of phosphorus(V) acid thioamides with 6h,ω-dihaloalkanes under phase-transfer
- Artyushin,Sharova,Petrovskii,Odinets
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experimental part
p. 216 - 222
(2010/06/12)
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- Asymmetric hydrogenation of enol phosphinates by iridium catalysts having N,P ligands
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Enol phosphinates, which are structural analogues of enol acetates, have for the first time been employed as substrates for Ir-catalyzed asymmetric hydrogenation. A number of enol phosphinates have been synthesized and reduced successfully with up to and above 99% ee.
- Cheruku, Pradeep,Gohil, Suresh,Andersson, Pher G.
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p. 1659 - 1661
(2008/02/02)
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- Design of a phosphinate-based fluorescent probe for superoxide detection in mouse peritoneal macrophages
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3′,6′-Bis(diphenylphosphinyl)fluorescein (PF-1) was synthesized as a highly selective and sensitive fluorescent probe for imaging O 2.- in living cells. The design strategy for the probe was based on the nucleophilic mechanism of O2.- to mediate deprotection of this probe to give fluorescein. Upon reaction with O 2.-, the probe exhibits a strong fluorescence response and high selectivity for O2.- over other reactive oxygen species and some biological compounds. The phosphinate-based probe, as a new fluorescent reagent, is cell-permeable and can detect micro molar changes of O2.- concentrations by using confocal microscopy in living cells. The unique combination of good selectivity, high sensitivity, good water solubility, and rapid reactivity establishes the potential value of the probe for facilitating investigations of the generation, metabolism, and mechanisms of superoxide-mediated cellular homeostasis and injury.
- Xu, Kehua,Liu, Xia,Tang, Bo,Yang, Guiwen,Yang, Yong,An, Liguo
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p. 1411 - 1416
(2008/02/04)
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- Aminophosphine oxides in a pyridine series. Studies on the cleavage of pyridine-2- and pyridine-4-yl-(N-benzylamino)-methyldiphenylphosphine oxides in acidic solutions
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The synthesis and reactions of 1-(N-benzylamino)-1-(2-pyridyl)- and 1-(N-benzylamino)-1-(4-pyridyl)-methyldiphenylphosphine oxides are described. It was found that these compounds were exceptionally easy to cleave in aqueous sulfuric acid solutions to form diphenylphosphinic acid and the corresponding N-(pyridylmethyl)-benzylamines. The structure of a single diastereoisomer, that is, the (R)-(+)-1-[N-(α-methylbenzylamino)]-1-(4-pyridyl)-(S)-methyldiphen ylphosphine oxide was determined by X-ray crystallography. The acidic alcoholysis of the selected model chiral pyridine aminophosphine oxides was investigated by means of 31P NMR spectroscopy. The cleavage kinetics were also studied. On the basis of the obtained results, a mechanism of the cleavage was formulated.
- Goldeman, Waldemar,Olszewski, Tomasz K.,Boduszek, Bogdan,Sawka-Dobrowolska, Wanda
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p. 4506 - 4518
(2007/10/03)
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- A versatile and efficient ligand for copper-catalyzed formation of C-N, C-O, and P-C bonds: Pyrrolidine-2-phosphonic acid phenyl monoester
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A new and readily available bidentate ligand, namely, pyrrolidine-2- phosphonic acid phenyl monoester (PPAPM), has been developed for the copper-catalyzed formation of C-N, C-O, and P-C bonds, and various N-, O-, and P-arylation products were synthesized in good to excellent yields by using the CuI/PPAPM catalyst system. Addition of the PPAPM ligand greatly increases the reactivity of the copper catalyst, and the resulting versatile and efficient catalyst system is of widespread and practical application in cross-coupling reactions.
- Rao, Honghua,Jin, Ying,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
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p. 3636 - 3646
(2008/02/03)
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- Pseudohalogenation of phosphites
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A new type of Atherton-Todd reaction for a convenient pseudohalogenation of phosphites has been developed. Direct azidation, cyanation, and thiocyanation of (RO)2P(O)H (R = Et, i-Bu, Ph) were accomplished readily with sodium pseudohalides in acetonitrile under mild modified Atherton-Todd conditions. The corresponding phosphorochloridates were demonstrated by GC/MS to be the intermediates. Pseudohalogenations of ethyl phenylphosphinate and diphenylphosphine oxide were also investigated.
- Shi, Enxue,Pei, Chengxin
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p. 2995 - 2998
(2007/10/03)
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- On the reactivity of the iminodiphosphane C6H 4(o-CN)N=PPh2-PPh2: Fragmentation versus isomerisation
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The reactivity of the iminodiphosphane C6H4(o-CN)N= PPh2-PPh2, which contains an N=P-P unit, has been investigated. Reaction with small molecules, [viz. H2P/O2, H2O2,
- Fei, Zhaofu,Scopelliti, Rosario,Dyson, Paul J.
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p. 530 - 537
(2007/10/03)
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- Phosphorus-containing compounds and uses thereof
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This invention concerns a new family of phosphorus-containing compounds containing a moiety JQA—in which: A is absent or is —O—, —S— or —NR2—; Q is absent or (if A is —O—, —S— or —NR2—) Q may be —V—, —OV—, —SV—, or —NR2V—, where V is an aliphatic, heteroaliphatic, aryl, or heteroaryl moiety, such that J is linked to the cyclohexyl ring directly, through A or through VA, OVA, SVA or NR2VA; K is O or S; each occurrence of Y is independently —O—, —S—, —NR2—, or a chemical bond linking a R5 moiety to P; and the other variables are as defined herein.
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- Synthesis of Racemic and Enantiomerically Pure (R*,R*,R* )-Tris(α-methylbenzyl)phosphane - X-ray Crystal Structures of the Phosphane Oxides and Borane Complexes
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An asymmetric synthesis of C3-symmetric phosphane 1 has been achieved. Two of the α-methylbenzyl groups were introduced as nucleophiles (using an α-methylbenzyl Grignard reagent), and asymmetry was introduced by resolution using (R)-α-methylbenzylamine. The final α-methylbenzyl group was introduced as an electrophile (α-methylbenzyl iodide) in a modestly selective reaction. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Wyatt, Paul,Eley, Helen,Charmant, Jonathan,Daniel, Berian J.,Kantacha, Anob
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p. 4216 - 4226
(2007/10/03)
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- Mixed anhydrides: Key intermediates in carbamates forming processes of industrial interest
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Mixed anhydrides of carbonic acid with phosphonic or carbamic acid, are mimic of relevant biological systems, and behave as key intermediates in transesterification processes that afford carbamates of industrial interest. They are formed in the phosphonic acids mediated or direct transesterification reaction of organic carbonates with amines to afford carbamates and have been isolated and characterised in the solid state and solution. Their conversion into the products has been demonstrated to occur with high regioselectivity. The application of such intermediates in some synthetic processes is discussed.
- Aresta, Michele,Dibenedetto, Angela
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p. 685 - 690
(2007/10/03)
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