- A Lewis Base Nucleofugality Parameter, NFB, and Its Application in an Analysis of MIDA-Boronate Hydrolysis Kinetics
-
The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured. Parameterization of these rates has enabled the development of a nucleofugality scale (NFB), shown to quantify and predict the leaving group ability of a range of other Lewis bases. Additivity observed across a number of series R′3-nRnX (X = P, N; R′ = aryl, alkyl) has allowed the formulation of related substituent parameters (nfPB, nfAB), providing a means of calculating NFB values for a range of Lewis bases that extends far beyond those experimentally derived. The utility of the nucleofugality parameter is explored by the correlation of the substituent parameter nfPB with the hydrolyses rates of a series of alkyl and aryl MIDA boronates under neutral conditions. This has allowed the identification of MIDA boronates with heteroatoms proximal to the reacting center, showing unusual kinetic lability or stability to hydrolysis.
- Taylor, Nicholas P.,Gonzalez, Jorge A.,Nichol, Gary S.,García-Domínguez, Andrés,Leach, Andrew G.,Lloyd-Jones, Guy C.
-
supporting information
p. 721 - 729
(2022/01/04)
-
- Palladium-Catalyzed C-P(III) Bond Formation by Coupling ArBr/ArOTf with Acylphosphines
-
Palladium-catalyzed C-P bond formation reaction of ArBr/ArOTf using acylphosphines as differential phosphination reagents is reported. The acylphosphines show practicable reactivity with ArBr and ArOTf as the phosphination reagents, though they are inert to the air and moisture. The reaction affords trivalent phosphines directly in good yields with a broad substrate scope and functional group tolerance. This reaction discloses the acylphosphines' capability as new phosphorus sources for the direct synthesis of trivalent phosphines.
- Chen, Xingyu,Wu, Hongyu,Yu, Rongrong,Zhu, Hong,Wang, Zhiqian
-
p. 8987 - 8996
(2021/06/30)
-
- Efficient potassium hydroxide promoted P-arylation of aryl halides with diphenylphosphine
-
A simple synthetic method of triarylphosphine compounds by KOH-promoted P-Arylation reaction of aryl halides with diphenylphosphine is presented. Notably, this transformation could smoothly proceed with high yields under transition-metal-free and mild reaction conditions. In addition, this protocol is valuable for industrial application due to the convenient operation and readily accessible aromatic halides. A possible explanation of the reaction mechanism was proposed based on the experimental data.
- Chen, Jin,Dai, Bencai,Liu, Changchun,Shen, Zhihao,Zhou, Yang
-
-
- Synthesis method of phosphine (III) compound
-
The invention aims to provide an aryl phosphine oxide compound as a raw material, wherein P=O keys are activated by an acid anhydride and alkali is continued. The preparation of the phosphine (III) compound is carried out under the action of a crown ether and a reducing agent. The method has the advantages of cheap and easily available raw materials, simple operation, high atomic economy and the like. Compared with a traditional reduction mode, the method is ingenious in design, waste emission is reduced, separation of intermediate products is omitted, and related reagents such as silicon hydrogen, aluminum, boron and the like with higher price can be avoided. And the reaction suitability is extensive.
- -
-
Paragraph 0020
(2021/11/27)
-
- Electron-rich triarylphosphines as nucleophilic catalysts for oxa-Michael reactions
-
Electron-rich triarylphosphines, namely 4-(methoxyphenyl)diphenylphosphine (MMTPP) and tris(4-trimethoxyphenyl)phosphine (TMTPP), outperform commonly used triphenylphosphine (TPP) in catalyzing oxa-Michael additions. A matrix consisting of three differently strong Michael acceptors and four alcohols of varying acidity was used to assess the activity of the three catalysts. All test reactions were performed with 1 mol % catalyst loading, under solvent-free conditions and at room temperature. The results reveal a decisive superiority of TMTPP for converting poor and intermediate Michael acceptors such as acrylamide and acrylonitrile and for converting less acidic alcohols like isopropanol. With stronger Michael acceptors and more acidic alcohols, the impact of the more electron-rich catalysts is less pronounced. The experimental activity trend was rationalized by calculating the Michael acceptor affinities of all phosphine-Michael acceptor combinations. Besides this parameter, the acidity of the alcohol has a strong impact on the reaction speed. The oxidation stability of the phosphines was also evaluated and the most electron-rich TMTPP was found to be only slightly more sensitive to oxidation than TPP. Finally, the catalysts were employed in the oxa- Michael polymerization of 2-hydroxyethyl acrylate. With TMTPP polymers characterized by number average molar masses of about 1200 g/mol at room temperature are accessible. Polymerizations carried out at 80°C resulted in macromolecules containing a considerable share of Rauhut-Currier-type repeat units and consequently lower molar masses were obtained.
- Boese, A. Daniel,Fischer, Susanne M.,Renner, Simon,Slugovc, Christian
-
supporting information
p. 1689 - 1697
(2021/08/03)
-
- Versatile Visible-Light-Driven Synthesis of Asymmetrical Phosphines and Phosphonium Salts
-
Asymmetrically substituted tertiary phosphines and quaternary phosphonium salts are used extensively in applications throughout industry and academia. Despite their significance, classical methods to synthesize such compounds often demand either harsh reaction conditions, prefunctionalization of starting materials, highly sensitive organometallic reagents, or expensive transition-metal catalysts. Mild, practical methods thus remain elusive, despite being of great current interest. Herein, we describe a visible-light-driven method to form these products from secondary and primary phosphines. Using an inexpensive organic photocatalyst and blue-light irradiation, arylphosphines can be both alkylated and arylated using commercially available organohalides. In addition, the same organocatalyst can be used to transform white phosphorus (P4) directly into symmetrical aryl phosphines and phosphonium salts in a single reaction step, which has previously only been possible using precious metal catalysis.
- Arockiam, Percia Beatrice,Lennert, Ulrich,Graf, Christina,Rothfelder, Robin,Scott, Daniel J.,Fischer, Tillmann G.,Zeitler, Kirsten,Wolf, Robert
-
supporting information
p. 16374 - 16382
(2020/11/03)
-
- Phosphine boranes as less hydrophobic building blocks than alkanes and silanes: Structure-property relationship and estrogen-receptor-modulating potency of 4-phosphinophenol derivatives
-
Increasing structural options in medicinal chemistry is important for the development of novel and distinctive drug candidates. In this study, we focused on phosphorus-containing functionalities. We designed and synthesized a series of phosphinophenol der
- Fujii, Shinya,Hashimoto, Yuichi,Matsumoto, Yuichiro,Saito, Hiroki
-
-
- Direct and Scalable Electroreduction of Triphenylphosphine Oxide to Triphenylphosphine
-
The direct and scalable electroreduction of triphenylphosphine oxide (TPPO)-the stoichiometric byproduct of some of the most common synthetic organic reactions-to triphenylphosphine (TPP) remains an unmet challenge that would dramatically reduce the cost and waste associated with performing desirable reactions that are mediated by TPP on a large scale. This report details an electrochemical methodology for the single-step reduction of TPPO to TPP using an aluminum anode in combination with a supporting electrolyte that continuously regenerates a Lewis acid from the products of anodic oxidation. The resulting Lewis acid activates TPPO for reduction at mild potentials and promotes P-O over P-C bond cleavage to selectively form TPP over other byproducts. Finally, this robust methodology is applied to (i) the reduction of synthetically useful classes of phosphine oxides, (ii) the one-pot recycling of TPPO generated from a Wittig reaction, and (iii) the gram-scale reduction of TPPO at high concentration (1 M) with continuous product extraction and in flow at high current density.
- Manabe, Shuhei,Sevov, Christo S.,Wong, Curt M.
-
p. 3024 - 3031
(2020/03/10)
-
- Copper-catalyzed C–P cross-coupling of secondary phosphines with (hetero)aromatic bromide
-
A novel and convenient approach to the synthesis of various tertiary phosphines via a copper-catalyzed cross-coupling of (hetero)aromatic bromide with secondary phosphines has been developed. The reaction employs cheap copper as the catalyst, 2,6-bis(N-methylaminomethyl)pyridine (L4) as a perfect ligand and KOtBu as a base; all reactions are carried out under argon atmosphere. A variety of sterically hindered and/or functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields. Moreover, ten new tertiary phosphines were first reported in this process.
- Li, Chun-Jing,Lü, Jing,Zhang, Zhi-Xun,Zhou, Kun,Li, Yan,Qi, Guang-Hui
-
p. 4547 - 4562
(2018/04/20)
-
- An efficient heterogeneous cross-coupling of aryl iodides with diphenylphosphine catalyzed by copper (I) immobilized in MCM-41
-
The heterogeneous cross-coupling reaction of aryl iodides with diphenylphosphine was achieved in toluene at 115?°C in the presence of 10?mol% of phenanthroline-functionalized MCM-41-supported copper (I) complex (Phen-MCM-41-CuI) with Cs2CO3 as base, yielding various unsymmetric triarylphosphines in good to excellent yields. This protocol can tolerate a wide range of functional groups and does not need the use of expensive additives or harsh reaction conditions. This heterogeneous Cu (I) catalyst exhibited the same catalytic activity as homogeneous CuI/Phen system, and could easily be recovered by a simple filtration of the reaction solution and recycled up to seven times without significant loss of activity.
- Fang, Zhiqiang,Cai, Mingzhong,Lin, Yang,Zhao, Hong
-
-
- A practical synthesis of unsymmetrical triarylphosphines by heterogeneous palladium(0)-catalyzed cross-coupling of aryl iodides with diphenylphosphine
-
The heterogeneous cross-coupling reaction of aryl iodides with diphenylphosphine was achieved in DMAc at 130 °C in the presence of 1.0 mol% of MCM-41-supported tridentate nitrogen palladium(0) complex [MCM-41-3N-Pd(0)] with KOAc as base, yielding a variety of unsymmetrical triarylphosphines in good to excellent yields. The turnover frequency (TOF) of the catalyst can reach 30.67 h?1. This new heterogeneous palladium(0) catalyst could easily be prepared by a simple procedure from commercially readily available reagents, and exhibited the same catalytic activity as homogeneous Pd(OAc)2 or Pd(PPh3)4, and could be recovered by filtration of the reaction solution and recycled at least seven times without significant loss of catalytic activity.
- Xu, Zhaotao,Wang, Pingping,Chen, Qiurong,Cai, Mingzhong
-
-
- Differentially Substituted Phosphines via Decarbonylation of Acylphosphines
-
A new route to phosphines was developed by a method that features a "pre-join and transform" process that proceeds via acylphosphine intermediates that may be readily prepared from carboxylic acids and disubstituted phosphines. The efficient decarbonylations of these acylphosphines using a nickel catalyst delivered the corresponding phosphines. This method shows that the carboxyl group can play a role similar to halides or triflates for introducing a substituted phosphorus atom on an aromatic ring.
- Yu, Rongrong,Chen, Xingyu,Martin, Stephen F.,Wang, Zhiqian
-
p. 1808 - 1811
(2017/04/11)
-
- Chemoselective Reduction of Phosphine Oxides by 1,3-Diphenyl-Disiloxane
-
Reduction of phosphine oxides to the corresponding phosphines represents the most straightforward method to prepare these valuable reagents. However, existing methods to reduce phosphine oxides suffer from inadequate chemoselectivity due to the strength of the P=O bond and/or poor atom economy. Herein, we report the discovery of the most powerful chemoselective reductant for this transformation to date, 1,3-diphenyl-disiloxane (DPDS). Additive-free DPDS selectively reduces both secondary and tertiary phosphine oxides with retention of configuration even in the presence of aldehyde, nitro, ester, α,β-unsaturated carbonyls, azocarboxylates, and cyano functional groups. Arrhenius analysis indicates that the activation barrier for reduction by DPDS is significantly lower than any previously calculated silane reduction system. Inclusion of a catalytic Br?nsted acid further reduced the activation barrier and led to the first silane-mediated reduction of acyclic phosphine oxides at room temperature.
- Buonomo, Joseph A.,Eiden, Carter G.,Aldrich, Courtney C.
-
supporting information
p. 14434 - 14438
(2017/10/23)
-
- Triaryl phosphine synthetic method (by machine translation)
-
The invention discloses a three-phosphine synthesis method, the method is that the diaryl phosphine oxygen, rich electronic aromatic hydrocarbon and the solvent is added in the reaction vessel, and finally adding trifluro anhydride stirring reaction; the temperature of the reaction after the end of the steaming and the solvent is removed, the silica gel column chromatography to obtain the three-phosphine. Compared with the conventional synthesis method, the method of the invention the reaction condition is simple, without any transition metal catalyst, reaction reagent is relatively safe and cheap, the reaction yield is high, good tolerance for the substrate and the like. (by machine translation)
- -
-
Paragraph 0016-0021
(2017/11/18)
-
- Synthesis method of carbonate modified fluoride-free organic phosphine ligand
-
The invention relates to the field of organic synthesis and provides a synthesis method of a carbonate modified fluoride-free organic phosphine ligand. The synthesis method comprises the following steps: preparing a Grignard reagent from the raw material p-bromoanisole or derivative thereof; enabling the Grignard reagent to react with a phosphorus source to generate a skeleton structure molecule with triphenylphosphine; and performing oxidation, demethylation, nucleophilic substitution and reduction to obtain a target molecular structure. The synthesis method has the following effects and benefits: a novel carbon dioxide-philic organic phosphine ligand is synthesized, the solubility of the phosphine ligand in supercritical CO2 is increased, and application of a fluoride-free phosphine ligand organic metal catalyst in supercritical CO2 is realized. Moreover, the organic carbonate compound is insoluble in a weakly (non-) polar organic solvent (such as alkane compounds), the property enables a phase splitting function of the carbonate modified fluoride-free organic phosphine ligand in the reaction system, and the recycling and reusing of the catalyst are realized.
- -
-
Paragraph 0041; 0042; 0053
(2017/08/28)
-
- Ligand-free palladium catalyzed phosphorylation of aryl iodides
-
A reusable ligand-free palladium catalyzed phosphorylation of aryl iodides using PdCl2/tetrabutylammonium bromide is described. Functionalized triarylphosphines were obtained in good to excellent yields in the absence of external reductants and supporting ligands.
- Nowrouzi, Najmeh,Keshtgar, Saba,Bahman Jahromi, Enayatollah
-
p. 348 - 350
(2016/01/12)
-
- Palladium-catalyzed C–P(III) bond formation reaction with acylphosphines as phosphorus source
-
Palladium-catalyzed C–P(III) bond formation reaction employing acylphosphines as the phosphorus source was developed. Under the optimized conditions, acylphosphines could react with aryl halides directly affording trivalent phosphines in up to 94% yield.
- Yu, Rongrong,Chen, Xingyu,Wang, Zhiqian
-
p. 3404 - 3406
(2016/07/11)
-
- Ternary donor-acceptor phosphine oxide hosts with peculiar high energy gap for efficient blue electroluminescence
-
Ternary donor (D)-acceptor (A)-acceptor (A) molecules are commonly considered as low triplet (T1) energy systems for specific applications. In this work, exception to this behavior was observed in a triangle-shaped D-A-A molecule PCImbPO with unusually high triplet energy of 3.0 eV. Profiting from the enhanced D-A electronic coupling, electron injecting and transporting ability of PCImbPO was dramatically improved with negligible influences on its highest occupied molecular orbital (HOMO) characteristics. Its particular T1 configuration adjustment further gives rise to the separated frontier MO and T1 locations, beneficial to suppress quenching effects. By utilizing PCImbPO as host in blue phosphorescent organic light-emitting diodes (PHOLEDs) and thermally activated delayed fluorescence devices, impressively high external quantum efficiency of 22% and 12% were achieved, respectively. This work established a new understanding of high-energy-gap complicated D-A systems.
- Sun, Mingzhi,Zhu, Liping,Kan, Wenjing,Wei, Ying,Ma, Dongge,Fan, Xuefeng,Huang, Wei,Xu, Hui
-
p. 9469 - 9478
(2015/09/15)
-
- PHOSPHONIUM COMPOUND OR INTERMOLECULAR SALT THEREOF, AND METHOD OF PRODUCING THE SAME
-
PROBLEM TO BE SOLVED: To provide a compound useful as a curing accelerator of an epoxy resin composition and a method of producing the same. SOLUTION: This invention provides a phosphonium compound represented by general formula (I-1) or intermolecular sa
- -
-
Paragraph 0068
(2016/10/08)
-
- Metal-free reduction of tertiary phosphine oxides with Hantzsch ester
-
The (COCl)2/Hantzsch ester is found to be an effective system for the metal-free reduction of tertiary phosphine oxides. The reaction proceeds under mild conditions, and is applicable to triarylphosphine oxides and alkyldiarylphosphine oxides to produce the corresponding tertiary phosphines in good to excellent yields. This new finding provides a practical, convenient and metal-free method for the reduction of tertiary phosphine oxides to tertiary phosphines, and shows potential application in organic synthesis.
- Zhang, Tong-Xin,Zhang, Wei-Xi,Luo, Mei-Ming
-
p. 176 - 178
(2014/02/14)
-
- General and selective copper-catalyzed reduction of tertiary and secondary phosphine oxides: Convenient synthesis of phosphines
-
Novel catalytic reductions of tertiary and secondary phosphine oxides to phosphines have been developed. Using tetramethyldisiloxane (TMDS) as a mild reducing agent in the presence of copper complexes, PO bonds are selectively reduced in the presence of other reducible functional groups (FGs) such as ketones, esters, and olefins. Based on this transformation, an efficient one pot reduction/phosphination domino sequence allows for the synthesis of a variety of functionalized aromatic and aliphatic phosphines in good yields.
- Li, Yuehui,Das, Shoubhik,Zhou, Shaolin,Junge, Kathrin,Beller, Matthias
-
supporting information; experimental part
p. 9727 - 9732
(2012/07/14)
-
- PHOSPHINE COMPOUND, PROCESS FOR PRODUCING THE SAME, AND PEROXIDE SCAVENGER USING THE SAME
-
The invention provides a novel peroxide scavenger comprising a phosphine compound represented by general formula [I]: wherein Z1 and Z2 each represents a cyclic group; Ar represents an arylene group; R represents an aliphatic hydrocarbon group; Y represents phosphorus (P), nitrogen (N), or bismuth (Bi); and R1, R2, and R3 each represents a cyclic group, particularly a peroxide scavenger that can scavenge peroxides such as reactive oxygen species which are generated in mitochondria upon exposure to oxidative stress and localized in mitochondria. The phosphine compound of the invention is oxidized by the peroxides localized in mitochondria to increase the fluorescence intensity, whereby the peroxides can be scavenged.
- -
-
Page/Page column 14
(2011/02/18)
-
- Novel phosphite palladium complexes and their application in C-P cross-coupling reactions
-
A mono- and a 1,3-bis-phosphite arene ligand based on 2,2′-biphenol have been synthesized in order to study the synthesis of the corresponding palladium(II) complexes starting from different Pd precursors. Novel bis-phosphite palladium complex 1 [PdCl2(L)2] (L = dibenzo[d,f][1,3,2]dioxaphosphepin, 6-phenoxy), C,P-chelate bonded monophosphite palladium complex 2 [Pd(κ2-L)(μ-Cl)]2, and PCP-pincer palladium complex 3 have been prepared from these ligands in promising to excellent yields (50-95%). Additionally, complexes 1 and 3 have been characterized by X-ray crystal structure determinations. The application of 2,6-bis-phosphite pincer palladium(II) complex 3 in C-P cross-coupling between diphenylphosphine-borane and a wide range of various aryl iodides under very mild conditions is reported. Kinetic investigations indicate that 3 merely acts as a pre-catalyst and that Pd nanoparticles are the actual catalytically active species.
- Li, Jie,Lutz, Martin,Spek, Anthony L.,Van Klink, Gerard P.M.,Van Koten, Gerard,Klein Gebbink, Robertus J.M.
-
experimental part
p. 2618 - 2628
(2010/11/21)
-
- Variable-temperature NMR studies of soluble polymer-supported phosphine-silver complexes
-
(Chemical Equation Presented) The use of polymers as supports for organometallic catalysts has received wide attention. However, catalyst reactivity is sometimes altered as a consequence of catalyst immobilization by a polymeric ligand and such altered reactivity can complicate such supported catalysts' use. The results in this study show that heptane phase selectively soluble polyisobutylene (PIB)-bound phosphine ligands have essentially identical kinetic behavior when compared to electronically similar isobutyldiphenylphosphine analogues in phosphine coordination and exchange in silver(I) halide complexes. These studies used variable-temperature 31P NMR spectroscopy to probe the silver-phosphine exchange processes for both AgI and AgCl complexes of these polymeric and low molecular weight phosphine ligands. The results show that the dynamic behavior of the PIB- and isobutyldiphenylphosphine-AgX complexes is nearly identical based on line-shape analysis of these 31P NMR spectra as a function of temperature. Similar studies of more polar poly(ethylene glycol)triarylphosphine-bound AgX complexes and electronically analogous low molecular weight AgX complexes have similar behavior in variable-temperature 31P NMR spectroscopy.
- Bergbreiter, David E.,Yang, Yun-Chin
-
experimental part
p. 873 - 878
(2010/04/30)
-
- Homolytic substitution at phosphorus for the synthesis of alkyl and aryl phosphanes
-
(Chemical Equation Presented) A transition-metal-free radical phosphonation using Me3SnPPh2 and the less toxic Me 3SiPPh2 is reported. These readily available reagents react highly efficiently with primary and secondary alkyl radicals. Moreover, aryl radicals and tertiary alkyl radicals are phosphonated with Me 3SnPPh2 (see scheme; R = aryl, alkyl, vinyl; X = 1, Br, OC(S)imidazolyl). DFT calculations provide insights into the mechanism of the reaction.
- Vaillard, Santiago E.,Mueck-Lichtenfeld, Christian,Grimme, Stefan,Studer, Armido
-
p. 6533 - 6536
(2008/09/17)
-
- Radical phosphination of organic halides and alkyl imidazole-1- carbothioates
-
Taking advantage of a radical-based methodology, mild and chemoselective phosphination reactions of organic halide and alkyl imidazole-1-carbothioates have been developed. The mild reaction conditions allow labile functional groups to survive during the reaction. Copyright
- Sato, Akinori,Yorimitsu, Hideki,Oshima, Koichiro
-
p. 4240 - 4241
(2007/10/03)
-
- Synthesis of symmetrical and unsymmetrical functionalized arylphosphines from chlorophosphines and organozinc reagents
-
A stepwise procedure allowing the formation of symmetrical arylphosphines is described. It relies on the use of preformed functionalized aromatic organozinc reagents to perform arylations of chlorophosphines. Some preliminary results concerning the synthesis of unsymmetrical diarylphenylphosphines through sequential coupling of organozinc species with dichlorophenylphosphine are also reported. Georg Thieme Verlag Stuttgart.
- Le Gall, Erwan,Ben A?ssi, Karima,Lachaise, Isabelle,Troupel, Michel
-
p. 954 - 956
(2007/10/03)
-
- Synthesis of aryl phosphines via phosphination with triphenylphosphine by supported palladium catalysts
-
The palladium catalyzed phosphination of functionalized aryl bromides, triflates, and chlorides with triphenylphosphine to yield aryldiphenylphosphines was catalyzed by thermally stable palladium catalysts supported on charcoal and aluminia. The addition
- Wang, Yanchun,Lai, Chi Wai,Kwong, Fuk Yee,Jia, Wen,Chan, Kin Shing
-
p. 9433 - 9439
(2007/10/03)
-
- Application of palladium-catalyzed Pd-aryl/P-aryl exchanges: Preparation of functionalized aryl phosphines by phosphination of aryl bromides using triarylphosphines
-
Palladium-catalyzed Pd-aryl/P-aryl interchange reaction was applied in the synthesis of various functionalized arylphosphines. This phosphination used inexpensive, readily available and air stable triarylphosphines as the phosphinating agents. Broad functional groups were compatible including keto, aldehyde, ester, nitrile, ether, chloride, pyridyl and thiophenyl groups. Halides were found to be good promoter for the rates and yields of the reaction.
- Kwong, Fuk Yee,Lai, Chi Wai,Yu, Michael,Chan, Kin Shing
-
p. 5635 - 5645
(2007/10/03)
-
- Nickel-catalyzed reductive coupling of chlorodiphenylphosphine with aryl bromides into functionalized triarylphosphines
-
Functionalized triarylphosphines are obtained with good yields in a one-step reaction of an equimolar mixture of chlorodiphenylphosphine and an aromatic bromide in NMP or DMF at 110°C in the presence of zinc dust and a catalytic amount of NiBr2
- Le Gall, Erwan,Troupel, Michel,Nédélec, Jean-Yves
-
p. 7497 - 7500
(2007/10/03)
-
- Palladium-catalyzed phosphination of functionalized aryl triflates
-
Catalytic user-friendly approach to the syntheses of various functionalized aromatic phosphines from their corresponding substituted aryl triflates and triarylphosphines was accomplished. This method is carried out in neutral media and compatible with man
- Kwong, Fuk Yee,Lai, Chi Wai,Yu, Michael,Tian, Yuan,Chan, Kin Shing
-
p. 10295 - 10305
(2007/10/03)
-
- Solvent-free palladium-catalyzed phosphination of aryl bromides and triflates with triphenylphosphine
-
Palladium-catalyzed phosphination of substituted aryl bromides and triflates using triphenylphosphine as the phosphinating agent was developed using solvent-free conditions. This operationally simple method tolerates ketone, aldehyde, ester, nitrile and e
- Kwong, Fuk Yee,Lai, Chi Wai,Chan, Kin Shing
-
p. 3537 - 3539
(2007/10/03)
-
- Synthesis of aryl phosphines by phosphination with triphenylphosphine catalyzed by palladium on charcoal
-
The palladium-catalyzed phosphination of aryl bromides and triflates by phosphination with triphenylphines to yield aryl phosphines was catalyzed by the thermally stable catalyst palladium on charcoal.
- Lai, Chi Wai,Kwong, Fuk Yee,Wang, Yanchun,Chan, Kin Shing
-
p. 4883 - 4885
(2007/10/03)
-
- A general synthesis of aryl phosphines by palladium catalyzed phosphination of aryl bromides using triarylphosphines
-
Palladium catalyzed phosphination of substituted aryl bromides using triarylphosphines as the phosphinating agents has been developed; this method tolerates ketone, aldehyde, ester, nitrile, ether and chloride functional groups.
- Kwong, Fuk Yee,Chan, Kin Shing
-
p. 1069 - 1070
(2007/10/03)
-
- A novel synthesis of functionalised tertiary phosphines by palladium catalysed phosphination with triarylphosphines
-
The palladium catalysed Pd-aryl/P-aryl exchange was applied in the synthesis of various functionalised phosphines from their corresponding substituted aryl triflates using triarylphosphines as the phosphinating agents. This method tolerated many functional groups including ketone, aldehyde, ester, nitrile, methyl ether, pyridyl and chloride groups. (C) 2000 Elsevier Science Ltd.
- Kwong, Fuk Yee,Lai, Chi Wai,Tian, Yuan,Chan, Kin Shing
-
p. 10285 - 10289
(2007/10/03)
-
- Electrosynthesis of triorganylphosphines from organic halides and chlorophosphines, catalyzed by nickel complexes
-
The possibility of cross coupling of organic halides and chlorophosphines under the action of electrochemically generated Ni(0) complexes of 2,2′-bipy is shown. The final triorganylphosphines are formed by several pathways, including reaction of the σ complex of ArNiX with chlorophosphine and electron transfer-induced reductive elimination of Ph2PArNiX, leading to the cross-coupling product.
- Budnikova,Kargin,Sinyashin
-
p. 524 - 528
(2007/10/03)
-
- Nickel-catalysed electrochemical coupling between mono- or di-chlorophenylphosphines and aryl or heteroaryl halides
-
Nickel-catalysed electrochemical cross-coupling between aryl- or heteroaryl-halides and chlorodiphenylphosphine or dichlorophenylphosphine affords tertiary phosphines in good to high yields.
- Budnikova, Yulia,Kargin, Yuri,Nedelec, Jean-Yves,Perichon, Jacques
-
-
- Wittig reactions in water. Synthesis of new water-soluble phosphonium salts and their reactions with substituted benzaldehydes
-
We report the synthesis of new phosphonium salts which are soluble and stable in basic aqueous solution. The Wittig reactions of these phosphonium salts with substituted benzaldehydes in aqueous sodium hydroxide are discussed. These reactions exclude the use of any organic solvents and the products are isolated by a simple filtration.
- Russell, Matthew G.,Warren, Stuart
-
p. 7995 - 7998
(2007/10/03)
-
- Photoinduced electron transfer between [Cu(dmphen)L2]+ [dmphen = 2,9-dimethyl-1,10-phenanthroline, L = PPhn(C6H4OMe-p)3-n (n = 0-3)] and methyl viologen
-
Photocatalytic reduction of methyl viologen (1,1′-dimethyl-4,4′-bipyridinium mv2+) was efficiently carried out with copper(I) complexes [Cu(dmphen)L2]+ [dmphen = 2,9-dimethyl-1,10-phenanthroline, L = PPhn(C
- Sakaki, Shigeyoshi,Mizutani, Hiroki,Kase, Yu-Ichi,Inokuchi, Ko-Ji,Arai, Toru,Hamada, Taisuke
-
p. 1909 - 1914
(2007/10/03)
-
- synthesis and Solid-State Structure of Substituted Arylphosphine Oxides
-
We described the preparation and characterization of several new arylphosphine oxides, which are of interest as second-order nonlinear optical materials. (4-Aminophenyl)diphenylphosphine oxide (1a), bis(4-aminophenyl)phenylphosphine oxide (2a), and (4-aminophenyl)bisphosphine oxide (5) were prepared by addition of aryl Grignard and organolithium reagents containing protected amines to phosphorus oxyhalides.Alternatively, 1a was prepared by treatment of (4-bromophenyl)diphenylphosphine oxide with azidomethyl phenyl sulfide, followed by hydrolysis. (4-Aminophenyl)(4'-nitrophenyl)phenylphosphine oxide (6) was prepared by nucleophilic aromatic substitution of bis(4-fluorophenyl)phenylphosphine oxide to give the corresponding dinitro compound, followed by selective mono-reduction.The X-ray crystal structure of (4-aminophenyl)diphenylphosphine oxide (1a), along with those of mono-, di-, and trihydroxy triphenylphosphine oxides 1b, 2b, and 3b, exhibit extensive intermolecular hydrogen bonding.The hydrogen bonding in 1a and 1b produces chains of arylphosphine oxide molecules with a head-to-tail alignment; the chains pack in an antiparallel manner to produce solid-state structures that display only slight deviations from centrosymmetry.
- Whitaker, Craig M.,Kott, Kevin L.,McMahon, Robert J.
-
p. 3499 - 3508
(2007/10/02)
-
- Substituent Effect in the Reaction of Triphenylphosphine with Diazodiphenylmethane: the Interpretation of a U-Shaped Hammett Correlation in an Elementary Biphilic Reaction
-
The reaction between diazodiarylmethanes and triphenylphosphine has previously been shown to be an elementary biphilic reaction in which each reactant behaves simultaneously as both electrophile and nucleophile.Frontier molecular orbital considerations pr
- Bethell, Donald,Bourne, Raymond,Kasran, Madzlan
-
p. 2081 - 2084
(2007/10/02)
-
- Aromatic Radical Nucleophilic Substitution Reactions Initiated by Sodium Amalgam in Liquid Ammonia
-
Neither 1-chloronaphthalene nor 2-chloroquinoline reacted with Ph2P- ions in liquid ammonia.However, in the presence of sodium amalgam , reaction did occur, and the substitution products 1-naphthyldiphenylphosphine and 2-quinolinyldiphenylphosphine (isolated as the P-oxides), respectively, were obtained in good yield. p-Bromoanisole reacted with Na(Hg) amalgam in the presence of Ph2C- ions in liquid ammonia to give anisole as the only product, but when benzonitrile was used as a redox catalyst, a good yield of the substitution product p-anisyldiphenylphosphine (isolated as the P-oxide) was obtained.It is believed that Na(Hg) amalgam initiated these SRN1 reactions.Preparative-scale reactions gave good yields of the substitution products.
- Austin, Eduardo,Alonso, Ruben A.,Rossi, Roberto A.
-
p. 4486 - 4489
(2007/10/02)
-
- Formation and Reactions of Diorganophosphinite Ions in Liquid Ammonia. Synthesis of Triorganophosphine Oxides by the SRN1 Mechanism
-
The reaction of triphenyl- and tribenzylphosphine oxides with alkali metals in liquid ammonia gave diphenyl- and dibenzylphosphinite ions, respectively, in high yields and a small amount of deoxygenated products.These ions reacted under photostimulation with aryl halides by the SRN1 mechanism to give aryldiphenyl- and aryldibenzylphosphine oxides in good yields.With tribenzylphosphine oxide, by consecutive debenzylation with alkali metals followed by photostimulated reaction with aryl halides, all the benzylic moieties could be replaced by aromatic moieties to finally obtain unsymmetrical triarylphosphine oxides.
- Bornancini, Estaban R. N.,Rossi, Roberto A.
-
p. 2332 - 2336
(2007/10/02)
-
- Palladium-Catalyzed Coupling of Aryl Halides with (Trimethylstannyl)diphenylphosphine and (Trimethylsilyl)diphenylphosphine
-
The palladium-catalyzed reaction of aryl halides with either (trimethylsilyl)diphenylphosphine or (trimethylstannyl)diphenylphosphine gives aryldiphenylphosphines in good yields, under relatively mild conditions (50-70 deg C, benzene).The reaction tolerates a number of functional groups including methyl ethers, esters, ketones, nitriles, anilides, and certain halogens.The nitro and aldehyde groups as well as compounds containing groups such as amino and hydroxyl are not tolerated.
- Tunney, S. E.,Stille, J. K.
-
p. 748 - 753
(2007/10/02)
-
- Relative Reactivity of 1-Adamantyl Radicals toward Diphenylphosphide and Benzenethiolate Ions
-
Competition experiments of diphenylphosphide (Ph2P-) and benzenethiolate (PhS-) ions toward p-anisyl radicals gave a kP/kS ratio of 52 in liquid ammonia.In competition experiments between the same nucleophiles toward 1-adamantyl radicals, the kP/kS ratio could not be determined in liquid amonia (>1000).These competition experiments were also performed in Me2SO, and p-anisyl radicals gave then kP/kS ratio of 8.4 and 1-adamantyl radicals a kP/kS ratio of 830.This difference in selectivity is attributed to the greater stability of 1-adamantyl radicals compared to that of p-anisyl radicals.Competition experiment of 1-bromoadamantane and p-bromoanisole toward Ph2P- ions gave almost the same reactivity (k(1-BrAd)/k(pBrAn)=0.96), suggesting that the radical anion intermediates in these reactions transfer their odd electrons to both substrates with similar rates.
- Bornancini, Esteban R. N.,Alonso, Ruben A.,Rossi, Roberto A.
-
p. 2166 - 2170
(2007/10/02)
-
- ONE POT SYNTHESIS FROM THE ELEMENTS OF SYMMETRICAL AND UNSYMMETRICAL TRIARYL-PHOSPINES, -ARSINES AND -STIBINES BY THE SRN1 MECHANISM
-
The reactions of elemental phosphorus, arsenic and antimony with sodium metal in liquid ammonia form "M-3" species that react with haloarenes under irradiation to form symmetrical triaryl derivatives of these metals by the SRN1 mechanism in fair to good yields.Further reaction with sodium metal gives a derivative nucleophile (diarylphosphide and diarylarsenide ions) that reacts with another haloarene under irradiation to form unsymmetrical phosphines and arsines.
- Bornancini, Esteban R.,Alonso, Ruben A.,Rossi, Roberto A.
-
p. 177 - 184
(2007/10/02)
-