- Phosphastannirane: A phosphorus/tin(II) lewis pair that undergoes alkyne and alkene addition
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Bermuda triangle: The first molecule containing a cyclic three-membered Sn-C-P ring has been synthesized and characterized. This SnII-P Lewis pair reacts at room temperature with alkynes and pentene to give the five-membered cyclic addition products. In the case of pentene, this reaction is reversible at room temperature. Trip=2,4,6-iPr3C6H 2. Copyright
- Freitag, Sarah,Henning, Jens,Schubert, Hartmut,Wesemann, Lars
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- Visible-Light-Promoted Unsymmetrical Phosphine Synthesis from Benzylamines
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Herein, by applying visible-light photoredox catalysis, we have achieved the catalytic deaminative alkylation of diphenylphosphine and phenyl phosphine with benzylamine-derived Katritzky salts at room temperature. The use of Eosin Y as photoredox catalyst and visible light can largely promote the reaction. A series of unsymmetrical tertiary phosphines were successfully synthesized, including phosphines with three different substituents that are otherwise difficult to obtain.
- Cui, Penglei,Li, Sida,Wang, Xianjin,Li, Ming,Wang, Chun,Wu, Lipeng
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supporting information
p. 1566 - 1570
(2022/03/01)
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- A Lewis Base Nucleofugality Parameter, NFB, and Its Application in an Analysis of MIDA-Boronate Hydrolysis Kinetics
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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.
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supporting information
p. 721 - 729
(2022/01/04)
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- Versatile Visible-Light-Driven Synthesis of Asymmetrical Phosphines and Phosphonium Salts
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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
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supporting information
p. 16374 - 16382
(2020/11/03)
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- Palladium-catalyzed C(sp3)–P(III) bond formation reaction with acylphosphines as phosphorus source
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Palladium-catalyzed C(sp3)–P(III) bond formation reaction for alkyl substituted phosphines preparation was developed. In this reaction, various alkyl bromides and limited alkyl chlorides reacted with acylphosphine under relative mild and easily accessible condition, and differential phosphines were afforded in good yields. This reaction made up the application of palladium catalysis in C(sp3)–P(III) bond formation, and indicated a practical application of acylphosphine as a phosphination reagent.
- Zhang, Mengyue,Ma, Zhichao,Du, Hongguang,Wang, Zhiqian
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- Bis(alkyl) scandium and yttrium complexes coordinated by an amidopyridinate ligand: Synthesis, characterization and catalytic performance in isoprene polymerization, hydroelementation and carbon dioxide hydrosilylation
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New neutral bis(alkyl) Sc and Y complexes [N,Npy,N-]Ln(CH2SiMe3)2(THF)n [n = 0, Ln = Sc (1Sc), Y (1Y); n = 1, Ln = Y (1YTHF)] stabilized by a tridentate monoanionic amidopyridinate ligand were straightforwardly prepared by alkane elimination, upon mixing ligand [N,Npy,N-]H and metal precursor Ln(CH2SiMe3)3(THF)2 in toluene at 0 °C. Depending on the work-up conditions, yttrium bis(alkyl)s were isolated as either a pentacoordinate Lewis base free complex [N,Npy,N-]Y(CH2SiMe3)2 (1Y) or as a hexacoordinate THF adduct [N,Npy,N-]Y(CH2SiMe3)2THF (1YTHF). For the smaller Sc ion the only solvent-free complex [N,Npy,N-]Y(CH2SiMe3)2 (1Sc) was isolated as a pentacoordinate species irrespective of the reaction/work-up/crystallization conditions applied. Complexes 1Ln (Ln = Y, Sc) and 1YTHF were scrutinized as pre-catalysts in ternary catalytic systems Ln/borate/AliBu3 (borate = [HNMe2Ph][B(C6F5)4] or [Ph3C][B(C6F5)4]), applied to isoprene (IP) polymerization, providing moderate activity albeit high selectivity with predominant formation of 1,4-cis polyisoprene (up to 99%). The same complexes proved to be effcient catalysts also for the intermolecular hydrolelementation of styrene with various EH sustrates (pyrrolidine, morpholine, Ph2PH, PhPH2, PhSH) affording linear anti-Markovnikov addition products exclusively. After a preliminary activation by B(C6F5)3, selected bis(alkyl) complexes from this series have been finally used as valuable pre-catalysts for the CO2 hydrosylilation to CH4 in the presence of organosilanes as reducing agents (PhMe2SiH, PhSiH3, Et2MeSiH).
- Gurina,Kissel,Lyubov,Luconi,Rossin,Tuci,Cherkasov,Lyssenko,Shavyrin,Ob'Edkov,Giambastiani,Trifonov
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p. 638 - 650
(2020/01/30)
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- Accessing Ambiphilic Phosphine Boronates through C?H Borylation by an Unforeseen Cationic Iridium Complex
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Ambiphilic molecules, which contain a Lewis base and Lewis acid, are of great interest based on their unique ability to activate small molecules. Phosphine boronates are one class of these substrates that have interesting catalytic activity. Direct access to these phosphine boronates is described through the iridium-catalyzed C?H borylation of phosphines. An unconventional cationic iridium catalyst was identified as optimal for a range of phosphines, providing good yields and selectivity across a diverse class of phosphine boronates (isolated as the borane-protected phosphine). A complimentary catalyst system (quinoline-based silane ligand with [(COD)IrOMe]2) was optimal for biphenyl-based phosphines. Selective polyborylation was also shown providing bis- and tris-borylated phosphines. Deprotection of the phosphine boronate provided free ambiphilic phosphine boronates, which do not have detectable interactions between the phosphorus and boron atoms in solution or the solid state.
- Wright, Shawn E.,Richardson-Solorzano, Stephanie,Stewart, Tiffany N.,Miller, Christopher D.,Morris, Kelsey C.,Daley, Christopher J. A.,Clark, Timothy B.
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supporting information
p. 2834 - 2838
(2019/02/05)
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- ORGANIC MAGNESIUM PHOSPHIDE AND MANUFACTURING METHOD THEREOF, ORGANIC MAGNESIUM PHOSPHIDE COMPLEX AND MANUFACTURING METHOD THEREOF, AND MANUFACTURING METHOD OF ORGANIC PHOSPHORUS COMPOUND USING SAID PHOSPHIDE
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An organic magnesium phosphide expressed by Formula (1) below and an organic magnesium phosphide complex expressed by Formula (9) below are provided, and a manufacturing method of organic phosphorus compound is characterized in that the above compounds used as a reagent is reacted with an electrophile: wherein R1 and R2 are each independently an aliphatic group, heteroaliphatic group, alicyclic group, or heterocyclic group, and X is chlorine, bromine, or iodine, wherein R3 and R4 are each independently an aliphatic group, heteroaliphatic group, aromatic group, alicyclic group, or heterocyclic group, and X and Y are each independently chlorine, bromine, or iodine.
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Paragraph 0199-0204
(2019/08/26)
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- Alcohol-based Michaelis-Arbuzov reaction: An efficient and environmentally-benign method for C-P(O) bond formation
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The famous Michaelis-Arbuzov reaction is extensively used both in the laboratory and industry to manufacture tons of widely-used organophosphoryl compounds every year. However, this method and the modified Michaelis-Arbuzov reactions developed recently still have some limitations. We now report a new alcohol-version of the Michaelis-Arbuzov reaction that can provide an efficient and environmentally-benign method to address the problems of the known Michaelis-Arbuzov reactions. That is, a wide range of alcohols can readily react with phosphites, phosphonites, and phosphinites to give all the three kinds of phosphoryl compounds (phosphonates, phosphinates, and phosphine oxides) using an n-Bu4NI-catalyzed efficient C-P(O) bond formation reaction. This general method can also be easily scaled up and used for further synthetic transformations in one pot.
- Ma, Xiantao,Xu, Qing,Li, Huan,Su, Chenliang,Yu, Lei,Zhang, Xu,Cao, Hongen,Han, Li-Biao
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p. 3408 - 3413
(2018/08/06)
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- Electrophilic Phosphonium Cation-Mediated Phosphane Oxide Reduction Using Oxalyl Chloride and Hydrogen
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The metal-free reduction of phosphane oxides with molecular hydrogen (H2) using oxalyl chloride as activating agent was achieved. Quantum-mechanical investigations support the heterolytic splitting of H2 by the in situ formed electrophilic phosphonium cation (EPC) and phosphane oxide and subsequent barrierless conversion to the phosphane and HCl. The reaction can also be catalyzed by the frustrated Lewis pair (FLP) consisting of B(2,6-F2C6H3)3 and 2,6-lutidine or phosphane oxide as Lewis base. This novel reduction was demonstrated for triaryl and diaryl phosphane oxides providing access to phosphanes in good to excellent yields (51–93 %).
- Stepen, Arne J.,Bursch, Markus,Grimme, Stefan,Stephan, Douglas W.,Paradies, Jan
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supporting information
p. 15253 - 15256
(2018/10/24)
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- Synthetic method of benzyl ligand applicable to hydroformylation
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The invention relates to a synthetic method of a benzyl ligand applicable to hydroformylation; the synthetic method is characterized by comprising the steps of adding 1.5 mol of n-hexane and 0.1-0.15 mol of methyl organic matter into a reaction container; adding suitable n-butyllithium, and heating the reaction container slowly to normal temperature; stirring at normal temperature for 20-30 hours; lowering the temperature of the reaction container to the range of -5 DEG C to 5 DEG C, and adding suitable compound with phosphorus chloride monomer slowly and evenly; heating the reaction container to normal temperature, stirring for 2-4 hours, and adding 0.4-1.0 mol of methanol and 0.8-1.2 mol of double distilled water slowly and evenly; separating the obtained mixture, and performing organic phase evacuating to obtain the benzyl ligand. The synthetic method is suitable for the preparation of compound molecules where the molecular structure contains one or more benzyl phosphine structural units.
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Paragraph 0015-
(2017/09/08)
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- Arene ci£h amination at nickel in terphenyl-diphosphine complexes with labile metal-arene interactions
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The meta-terphenyl diphosphine, m-P2, 1, was utilized to support Ni centers in the oxidation states 0, I, and II. A series of complexes bearing different substituents or ligands at Ni was prepared to investigate the dependence of metal-arene interactions on oxidation state and substitution at the metal center. Complex (m-P2)Ni (2) shows strong Ni 0-arene interactions involving the central arene ring of the terphenyl ligand both in solution and the solid state. These interactions are significantly less pronounced in Ni0 complexes bearing L-type ligands (2-L: L=CH3CN, CO, Ph2CN2), NiIX complexes (3-X: X=Cl, BF4, N3, N3B(C 6F5)3), and [(m-P2)Ni IICl2] (4). Complex 2 reacts with substrates, such as diphenyldiazoalkane, sulfur ylides (Ph2Si£CH2), organoazides (RN3: R=para-C6H4OMe, para-C 6H4CF3, 1-adamantyl), and N2O with the locus of observed reactivity dependent on the nature of the substrate. These reactions led to isolation of an η1-diphenyldiazoalkane adduct (2-Ph2CN2), methylidene insertion into a Nii£P bond followed by rearrangement of a nickel-bound phosphorus ylide (5) to a benzylphosphine (6), Staudinger oxidation of the phosphine arms, and metal-mediated nitrene insertion into an arene Ci£H bond of 1, all derived from the same compound (2). Hydrogen-atom abstraction from a NiI-amide (9) and the resulting nitrene transfer supports the viability of Ni-imide intermediates in the reaction of 1 with 1-azido-arenes. Put a ring on it: The utilization of a meta-terphenyl diphosphine ligand leads to labile metal-arene interactions in Ni complexes in various oxidation states and coordination environments. When these complexes are treated with group-transfer reagents, such as diazoalkanes, sulfur ylides, or azides, various types of ligand-centered reactivity were observed, including methylidene insertion into a Pi£C bond and amination of an arene Ci£H bond. Copyright
- Herbert, David E.,Lara, Nadia C.,Agapie, Theodor
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supporting information
p. 16453 - 16460
(2013/12/04)
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- Ph2PI as a reduction/phosphination reagent: Providing easy access to phosphine oxides
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The reaction of aldehydes with Ph2PI provides a facile way to the synthesis of pentavalent phosphine compounds with moderate to good yields.
- Wang, Feijun,Qu, Mingliang,Chen, Feng,Xu, Qin,Shi, Min
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supporting information; experimental part
p. 8580 - 8582
(2012/09/22)
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- Synthesis and structure of intermediates in copper-catalyzed alkylation of diphenylphosphine
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Cu(I) catalysts for alkylation of diphenylphosphine were developed. Treatment of [Cu(NCMe)4][PF6] (1) with chelating ligands gave [CuL(NCMe)][PF6] (2; L = MeC(CH2PPh2) 3 (triphos), 3; L = 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (XantPhos)). These complexes catalyzed the alkylation of PHPh2 with PhCH2Br in the presence of the base NaOSiMe3 to yield PPh2CH2Ph (4). The precursors Cu(dtbp)(X) (dtbp =2,9-di-t-butylphenanthroline, X = Cl (5) or OTf (6)), CuCl, and 1 also catalyzed this reaction, but dtbp dissociated from 5 and 6 during catalysis. Both 2 and 3 also catalyzed alkylation of PHPh2 with PhCH 2Cl/NaOSiMe3, but XantPhos dissociation was observed when 3 was used. When CH2Cl2 was used as the solvent for alkylation of PhCH2Cl with precursors 2 or 3, or of PhCH(Me)Br with 2, it was competitively alkylated to yield PPh2CH2Cl (7), which was formed exclusively using 2 in the absence of a benzyl halide. Cu(triphos)-catalyzed alkylation of PhCH(Me)Br gave mostly PPh2CHMePh (8), along with some Ph2P-PPh2 (9), which was also formed in attempted alkylation of dibromoethane with this catalyst. The phosphine complexes [Cu(triphos)(L′)][PF6] (L′ = PH2Ph (10), PH2CH2Fc (Fc = C5H4FeC 5H5, 11), PHPh2 (12), PHEt2 (13), PHCy2 (Cy = cyclo-C6H11, 14), PHMe(Is) (Is = 2,4,6-(i-Pr)3C6H2, 15), PPh2CH 2Ph (16), PPh2CH2Cl (17)), and [Cu(XantPhos)(L′)][PF6] (L′ = PHPh2 (18), PPh2CH2Ph (19)) were prepared by treatment of 2 and 3 with appropriate ligands. Similarly, treatment of dtbp complexes 5 or 6 with PHPh2 gave [Cu(dtbp)(PHPh2)(X)] (X = OTf (20a) or Cl (20b)), and reaction of PPh2CH2Ph (4) with 1 formed [Cu(PPh2CH2Ph)3][PF6] (21). Complexes 2, 3, 11-14, 16, 17, 19, and 21 were structurally characterized by X-ray crystallography. Deprotonation of diphenylphosphine complex 12 in the presence of benzyl bromide gave diphenylbenzylphosphine complex 16, while deprotonation of 12 in CD2Cl2 gave 17 containing a PPh2CD2Cl ligand. Low-temperature deprotonation of the soluble salt 12-[B(ArF)4] (ArF = 3,5-(CF 3)2C6H3) in THF-d8 gave the phosphido complex Cu(triphos)(PPh2) (22). Thermally unstable 22 was characterized by NMR spectroscopy and, in comparison to 12, by density functional theory (DFT) calculations, which showed it contained a polarized Cu-P bond. The ligand substitution step required for catalytic turnover was observed on treatment of 16 or 17 with PHPh2 to yield equilibrium mixtures containing 12 and the tertiary phosphines 4 or 7; equilibrium constants for these reactions were 8(2) and 7(2), favoring complexation of the smaller secondary phosphine in both cases. These observations are consistent with a proposed mechanism for catalytic P-C bond formation involving deprotonation of the cationic diphenylphosphine complex [Cu(triphos)(PHPh2)][PF 6] (12) by NaOSiMe3 to yield the phosphido complex Cu(triphos)(PPh2) (22). Nucleophilic attack on the substrate (benzyl halide or CH2Cl2) then yields the tertiary phosphine complex [Cu(triphos)(PPh2CH2X)][PF6] (X = Ph (16) or Cl (17)), and ligand substitution with PHPh2 regenerates 12.
- Cain, Matthew F.,Hughes, Russell P.,Glueck, David S.,Golen, James A.,Moore, Curtis E.,Rheingold, Arnold L.
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scheme or table
p. 7650 - 7662
(2010/11/19)
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- Synthesis of alkyl- and aryldiphenylphosphines via electrogenerated magnesium chloride diphenylphosphanide
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A two-steps procedure allowing the formation of alkyldiphenylphosphines and aryldiphenylphosphines in good yield is described. It relies on the electrochemical preparation of magnesium chloride diphenylphosphanide and its subsequent coupling with either alkyl halides or aryl fluorides.
- Nechab, Malek,Le Gall, Erwan,Troupel, Michel,Nédélec, Jean-Yves
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p. 1809 - 1813
(2007/10/03)
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- Phosphorus-carbon bond formation catalysed by electrophilic N-heterocyclic phosphines
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A P-chloro-diazaphospholene catalyses the phosphorus-carbon bond formation reaction between diphenylsilylphosphine and various alkyl chlorides. The Royal Society of Chemistry 2006.
- Burck, Sebastian,Foerster, Daniela,Gudat, Dietrich
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p. 2810 - 2812
(2008/09/19)
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- CsOH-promoted P-alkylation: A convenient and highly efficient synthesis of tertiary phosphines
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A mild and efficient method for the synthesis of tertiary phosphines and ditertiary phosphines has been developed. In the presence of cesium hydroxide, molecular sieves and DMF at room temperature, various secondary phosphines and alkyl bromides were examined, and the results have demonstrated that this methodology offers a general synthetic procedure to produce tertiary phosphines in moderate to high yields. Optically active tertiary phosphine synthesis is also described.
- Honaker, Matthew T.,Sandefur, Benjamin J.,Hargett, James L.,McDaniel, Alicia L.,Salvatore, Ralph Nicholas
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p. 8373 - 7377
(2007/10/03)
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- Ortho-Lithiated benzyl diorganophosphines [o-(R2PCH2)C6H4Li(Et2O)], R=Ph, Me. Synthesis, structural characterization, and reactions
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(o-Lithiobenzyl)dimethylphosphine, [o-(Me2PCH2)C6H4Li(Et 2O)]2 (7), is shown by crystal structure analysis to be dimeric, the two lithium atoms bridging the phenyl ortho-carbon atoms in a four-membered ring structure. A distorted tetrahedral coordination sphere at lithium is completed by coordination of one phosphino group and a molecule of diethylether (triclinic, space group P1?, a=10.986(3), b=11.160(3), c=12.368(4) ?, α=86.04(2), β=89.51(2), γ=83.04(2)°, Z=2). [o-(Me2PCH2)C6H4Li(Et 2O)]2 (7) cleanly reacts in donor solvents like diethylether to the thermodynamically more stable (α-lithiobenzyl)dimethylphosphine [Me2PCHLi(Et2O)C6H5]2 (9) with the same overall composition. Crystal structure analysis of the latter shows each lithium atom to be now bonded in an η2 fashion to the Cbenzyl-Cipso bond of one anion, the diethylether molecule, and to the phosphino group of the second anion thereby resulting in a dimeric structure with a central six-membered ring (triclinic, space group P1?, a=8.482(3), b=9.388(3), c=9.482(3) ?, α=95.42(2), β=91.36(2), γ=104.20(2)°, Z=1). (o-Lithiobenzyl)diphenylphosphine undergoes the same reaction to the corresponding α-lithiobenzylphosphine upon addition of strong donors like N,N,N′,N′-tetramethylethylenediamine (tmeda). Upon addition of Cp2TiCl2, (o-lithiobenzyl)diphenylphosphine reacts to form 1,2-bis[o-(diphenylphosphino)phenyl]ethane, [o-(Ph2P)C6H4CH2]2 (10), the formation of which is thought to proceed by oxidation of the anion [o-(Ph2PCH2)C6H4]- by Cp2TiCl2 to the radical which undergoes a 1,3 shift of the diphenylphosphino group from the sp3 benzyl carbon atom to the sp2 ortho-carbon atom of the phenyl ring to form the more stable benzyl radical. Dimerization of the latter ultimately leads to [o-(Ph2P)C6H4CH2]2 (10) whose molecular structure was determined in the solid state (monoclinic, space group P21/n, a=12.217(2), b=8.382(1), c=15.004(2) ?, β=90.81(1)°, Z=2). The same reaction occurs upon oxidation of (o-lithiobenzyl)diphenylphosphine with ferricinium tetrafluoroborate, [Cp2Fe]+BF4-, thus corroborating the proposed reaction sequence with the transition metal species acting solely as oxidizing agents.
- Müller, Gerhard,Abicht, Hans-Peter,Waldkircher, Martin,Lachmann, Joachim,Lutz, Martin,Winkler, Martin
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p. 121 - 134
(2007/10/03)
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- Olefination reactions through phosphazenes
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The first synthesis of di-, tri- and tetrasubstituted alkenes through reaction of lithium P-diphenyl(alkyl)(N-carboxymethyl)phosphazenes with aldehydes and ketones is reported.
- Perez,Ortiz
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p. 2029 - 2030
(2007/10/03)
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- Method for preparation of tertiary phosphines via nickel-catalyzed cross coupling
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The invention is an improved method for the preparation of tertiary phosphines by way of cross-coupling of aryl, alkenyl, cycloalkenyl or aralkyl halides or aryl, alkenyl, cycloalkenyl or aralkyl sulfonate esters with chlorophosphines in the presence of a
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- New chiral expanded phosphanes derived from substituted deltacyclenes
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The suitability of enantiomerically pure deltacyclenes as building blocks in the synthesis of expanded phosphanes was examined. Different substituted deltacyclenes were irradiated with diphenylphosphane and three bisphosphanyl derivatives. With these P-H addition reactions, new chiral del-tacyclane-derived phosphorus ligands were synthesized. They were tested in the Rh-catalyzed asymmetric hydroge nation of (Z)-(α)-N-acetamidocinnamic acid and in the Pdcatalyzed asymmetric allylation of 1,5-dimethylbarbituric acid. WILEY-VCH Verlag GmbH,.
- Brunner, Henri,Reimer, Alfred
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p. 1495 - 1498
(2007/10/03)
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- ZUR REAKTION VON PHOSPHORVERBINDUNGEN MIT SCHWESINGER BASEN-I P-C-BINDUNGKNUEPFUNG AN P-H-FUNKTIONELLEN PHOSPHORVERBINDUNGEN
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Secondary and tertiary phosphines (RR'PH; R2R'P) may be synthesized by alkylation of primary or secondary phosphines with organo halides (R' = Et, n-C7H15, Bz, Me3Si; X = Cl, Br) in the presence of Schwesinger bases as auxillary bases in high yields.Alkylation of diphenylphosphine with alkylene dihalides and Schwesinger bases affords alkylendiphosphines. Key words: Alkylation; secondary and tertiary phosphines; Schwesinger bases.
- Uhlig, Frank,Puschner, Beatrix,Herrmann, Eckhard,Zobel, Bernhard,Bernhardt, Henry,Uhlig, Wolfram
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p. 155 - 164
(2007/10/02)
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- Reductive cleavage of the carbon-phosphorus bond with alkali metals. III Reactions of arylalkylphosphines
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The reductive cleavage of phenylalkylphosphines Ph2PR, PhPR2 (R = Bu, iPr) with Na/NH3 is unselective; both phenyl and alkyl groups can be cleavaged and Birch reduction may occur.Reaction of Ph2tBuP gives a high yield of diphenylphosphide.Polar groups (CO2Na, SO3Na) at the ω position of primary alkyl groups may lead to an increase in selectivity; Birch reduction is suppressed and a functionalised secondary phosphide is obtained.From diarylbenzyl- and diarylallylphosphines, the benzyl and allyl groups are selectively removed; Ar2PH and ArRPH are formed in high yield after hydrolytic work-up unless the aryl group bears F, CF3 or (CH3)2N substituents.From the reaction mixture of Ph2PCH2Ph we have isolated 1,2-diphenylethane. 2-Methoxyphenyl and 2,6-dimethoxyphenyl groups are selectively removed from Ar2BuP, ArPhBuP and Ar2P(CH2)3PAr2, forming ArBuPH, PhBuPH and ArP(H)(CH2)3(H)PAr, respectively.A double-cleavage reaction of Ar2RP may occur in low yield. 2,6-(dimethoxyphenyl-dibutylphosphine gives dibutylphosphine in moderate yield.When compounds with a 2,6-dimethoxyphenyl moiety are allowed to react with Li/THF, removal of a methyl group leads to novel phosphinophenols.It is concluded that cleavage of alkyl groups R selectively occurs when R radical is relatively stable (tBu, PhCH2> iPr > Bu).
- Doorn, Johannes A. van,Meijboom, Nico
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p. 170 - 177
(2007/10/02)
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- THE REACTION OF DIBENZYLMERCURY WITH SECONDARY PHOSPHINES: PHOSPHORUS-PHOSPHORUS BOND FORMATION VERSUS BENZYL SUBSTITUTION
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In an attempt to find a simple, high yield synthetic method to create a phosphorus-phosphorus bond from phosphorus-hydrogen bonds, we have investigated the reaction of dibenzylmerury DBM with secondary phosphines.The overall reaction is: DBM + R2PH -> toluene + Hg + R2P-PR2.Thus reaction of diphenylphosphine with DBM produces the desired coupled product tetraphenyl diphosphine in 85-90percent yield.In contrast, the reaction of DBM with 1,3-bis(phenylphosphino)propane Ph(H)P-(CH2)3-P(H)Ph produces the benzyl-substituted product rather than the expected cyclic compound 1,2-diphenyl-1,2-diphospholane PhP-(CH2)3-PPh.The dioxide or disulfide of Ph(H)P-(CH2)3P(H)Ph undergoes no reaction with DBM.The bulky 2,4,6-tris(tert-butyl)phenylphosphine ArPH2 with DBM yields diastereomers of the coupled disecondary diphosphine Ar(H)P-P(H)Ar.The reaction of DBM with diphenylchlorophosphine results in a high yield of tetraphenyl diphosphine, but with phenyldichlorophosphine produces the benzyl-substituted product phenylbenzylchlorophosphine.
- Yeh, Jesse T.,Avens, Larry R.,Mills, Jerry L.
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p. 319 - 323
(2007/10/02)
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- Thermal Stability of Phosphinoacetic Acids
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Phosphinoacetic acids decarboxylate smoothly in toluene solution at 99 deg C and the corresponding alkylphosphine is formed in quantitative yields.Electron-withdrawing substituents at the α position of the carboxylic acid lead to a large increase in the reaction rate.In contrast, electron-withdrawing substituents at the phosphorus atom lead to a small decrease in the rate.We have concluded from the substituent effects, solvent effects, and the influence of bases and acids that both the lone pair of the phosphorus atom and the carboxylate hydrogen atom play a crucial role in the reaction.A mechanism is proposed that proceeds via an ylide.Sodium phosphinocarboxylates do not decarboxylate in an aqueous solution at 95 deg C.Instead a carbon-phosphorus bond cleavage occurs probably by an intramolecular nucleophilic substitution.
- Doorn, Johannes A. van,Meijboom, Nico
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p. 1309 - 1314
(2007/10/02)
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- ELECTROCHEMICAL SYNTHESIS OF TERTIARY PHOSPHINES FROM ORGANIC HALIDES AND CHLOROPHOSPHINES
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The electrochemical synthesis of a wide range of tertiary mono- and diphosphines has been achieved in very simple and mild conditions, in an undivided electrolytic cell with a sacrificial anode of magnesium.
- Folest, J. C.,Nedelec, J. Y.,Perichon, J.
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p. 1885 - 1886
(2007/10/02)
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- SYNTHESIS AND REACTIVITY OF UNSATURATED BIPHOSPHONIUM SALTS
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The synthesis of 1,2 vinylene biphosphonium salts 1 has now benn enlarged to the vinylogous 1,4-butadienylene biphosphonium salts 2.The salts 2, a new class of unsaturated disalts, have also been prepared through a two-step isomerisation of acetylenic sal
- Cristau, Henri-Jean,Duc, Gerald,Labaudiniere, Lydie,Pietrasanta, Francine,Plenat, Francoise
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p. 113 - 116
(2007/10/02)
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- Carbon Acidity. 63. Equilibrium Ion Pair Acidities of Some Phosphorus-Substituted Carbon Acids
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Ion-pair C-H acidities are reported as pKCsCHA for bis(diphenylphosphino)methane (1, 31.1), (p-phenylbenzyl)diphenylphosphine (3, 31.0), p-tolyldiphenylphosphine (4, 37.9), and several of the corresponding phosphine oxides.The diphenylphosphine group is about as anion stabilizing as p-biphenyl.The Ph2P(O) group is additionally stabilizing because of enhanced ion-pair interaction.The pKCsCHA of benzyldiphenylphosphine (2) can be estimated to be about 32.
- Streitwieser, Andrew,Juaristi, Eusebio
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p. 768 - 770
(2007/10/02)
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- ORGANOARSENEVERBINDUNGEN: 39 SUBSTITUERTE BENZYLPHOSPHINE UND -ARSINE ALS LEICHT ZUGAENGLICHE BIDENTATE LIGANDEN
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2-Hydroxybenzylamines or 2- and 4-aminobenzylamines react with diphenylphosphine at higher temperature to give hydroxy-substituted and aminosubstituted benzylphosphines, respectively.This reaction fails in the case of alkoxy or dialkylaminobenzyl amines.T
- Kellner, K.,Rothe, S.,Steyer, E.-M.,Tzschach, A.
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p. 269 - 274
(2007/10/02)
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