- Compound containing phosphine chiral center, organic transition metal complex and preparation method thereof
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The invention provides a compound containing a phosphine chiral center, an organic transition metal complex and a preparation method thereof. The preparation method of the compound comprises the following steps: (1) reducing a secondary phosphine oxide 1 into a product secondary phosphine hydrogen 2 by using a reducing agent, wherein the reaction temperature is 20 to 100 DEG C, and the reaction time is 12 to 120 hours; and (2) adding alkyne and the secondary phosphine hydrogen prepared in the step (1) into an organic solvent by using a metal catalyst and a chiral ligand as catalysts to obtain the chiral phosphine compound. The synthesized chiral phosphine compound can be used as a ligand to directly react with transition metal salt to synthesize various organic transition metal complexes. According to the synthesis method disclosed by the invention, secondary phosphine oxide with good stability and low odor is used as a raw material, so that direct use of secondary phosphine with high toxicity and odor for reaction is avoided, and the chiral trivalent phosphine product and the derivative thereof are efficiently and selectively obtained.
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Paragraph 0049-0053
(2021/07/10)
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- Ni-Catalyzed Asymmetric Hydrophosphination of Unactivated Alkynes
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The practical synthesis of P-stereogenic tertiary phosphines, which have wide applications in asymmetric catalysis, materials, and pharmaceutical chemistry, represents a significant challenge. A regio- and enantioselective hydrophosphination using cheap a
- Gao, Li,Han, Xue-Yu,Huang, Zhuo,Liu, Xu-Teng,Sun, Ying-Ying,Wu, Yue,Zhang, Qing-Wei
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supporting information
p. 11309 - 11316
(2021/08/03)
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- Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride
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A variety of phosphine oxides and sulfides can be efficiently converted directly to the corresponding phosphine boranes using oxalyl chloride followed by sodium borohydride. Optically active P-stereogenic phosphine oxides can be converted stereospecifically to phosphine boranes with inversion of configuration by treatment with Meerwein's salt followed by sodium borohydride.
- Rajendran, Kamalraj V.,Gilheany, Declan G.
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p. 817 - 819
(2012/02/03)
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- P-stereogenic ferrocene-based (Trifluoromethyl)phosphanes: Synthesis, structure, coordination properties and catalysis
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Diastereoselective ortho-hydroxymethylation of (R)-(1-ferrocenylethyl) dimethylamine and Bronsted-acid-mediatednucleophilic substitution with phenyl(trifluoromethyl)phosphane affords an epimeric mixture of P-stereogenic amine-phosphanes 4a and 4b, which a
- Sondenecker, Aline,Cvengros, Jan,Aardoom, Raphael,Togni, Antonio
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experimental part
p. 78 - 87
(2011/03/18)
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- Reduction of phosphinites, phosphinates, and related species with DIBAL-H
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Diisobutylaluminium hydride has been found to be an excellent reducing agent for phosphinites, phosphinates, and chlorophosphines. By performing reductions in situ, direct synthesis of secondary phosphine boranes from Grignard reagents has been achieved without isolation or purification of any intermediates. Georg Thieme Verlag Stuttgart.
- Busacca, Carl A.,Bartholomeyzik, Teresa,Cheekoori, Sreedhar,Raju, Ravinder,Eriksson, Magnus,Kapadia, Suresh,Saha, Anjan,Zeng, Xingzhong,Senanayake, Chris H.
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scheme or table
p. 287 - 291
(2009/07/01)
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- PHOSPHINE TRANSITION METAL COMPLEX, PROCESS FOR PRODUCING THE SAME AND ANTICANCER DRUG CONTAINING THE SAME
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There is provided a novel transition metal phosphine complex having excellent anticancer activity. The transition metal phosphine complex is represented by general formula (1): (wherein R1s and R3s each represent an alkyl group, a cy
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Page/Page column 11
(2008/06/13)
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- High atom-economical one-pot synthesis of secondary phosphines and their borane complexes using recycling phosphorus donor reagent
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A general new method for the one-pot preparation of secondary phosphines 11 and in situ generation of their borane complexes 12 is described. This method consists of the sequential addition, at room temperature, of equivalent amounts of R1MgBr and R2MgBr to 1 equiv of the phosphorus atom donor reagent 1. Final treatment with water gives secondary phosphines R 1R2PH (or the corresponding phosphine-borane complexes if treated with BH3·THF) and the end product 6, which can be recycled.
- Baccolini, Graziano,Boga, Carla,Mazzacurati, Marzia,Sangirardi, Federico
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p. 1677 - 1680
(2007/10/03)
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- Processes for producing secondary phosphines
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A process for producing a secondary phosphine of formula (2) wherein R1 and R2 may be the same or different and each represent an alkyl group, a cycloalkyl group or an aryl group, each of the above groups being optionally substituted by an alkyl group, an alkoxy group, a halogen atom, a perfluoroalkyl group, an amino group or a phosphino group, which comprises reacting a phosphine halide of formula (1) wherein R1 and R2 are as defined above and X represents a halogen atom, with a metal selected from the metals of Groups 2 to 15 in the Periodic Table or an alloy thereof and reacting the resultant metal di-substituted phosphide with an agent for protonation.
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- Resolution of secondary phosphanes chiral at phosphorus by means of palladium metallacycles
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The synthesis of new epimeric compounds [PdCl(C-N){(±)-PHPhR}] (C-N = (R)-C10H6CHMeNH2 and (R)-C6H4CHMeNH2, R = Me and PhCH2) containing chiral secondary phosphanes is reported. Some of these diastereomers can be separated by column chromatography; subsequent re- action of these complexes with 1,2-bis(diphenyiphosphanyl)-ethane (dppe) affords the free phosphanes PHBzPh and PHMePh. The configurational stability of the secondary phosphanes resolved has also been studied.
- Albert, Joan,Cadena, J. Magali,Granell, Jaume,Muller, Guillermo,Panyella, David,Sanudo, Carolina
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p. 1283 - 1286
(2007/10/03)
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- Dimethylsulfonium Methylide as a Methylating Agent for Three-Coordinate Phosphorus Derivatives
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Dimethylsulfonium methylide methylates primary alkyl- and arylphosphines and some secondary phosphines containing at least one substituent that does not exhibit donating properties with respect to phosphorus to give corresponding methylphosphines in high yield. The reaction proceeds as a two-step process with initial deprotonation of the phosphine with the ylide and subsequent nucleophilic elimination of the sulfonium salts with the phosphide. The second step determines the overall reaction rate.
- Veits,Chuchuryukin
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p. 235 - 238
(2007/10/03)
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- STRUTURAL CHARACTERIZATION OF 1,2,4,5-TETRAPHENYLCYCLO-3,6-DICARBA-1,2,4,5-TERAPHOSPHINE: A HIGHLY FOLDED CHAIR CONFORMATION
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The title compound crystallyzed in the monoclynic space group P21/c, with the followingunit cell parameters: a = 11.235(8), b = 8.473(2), c = 26.136(10) Aengstroem, β = 102.07(5) grad, V = 2432(3) Aengstroem3, Z = 4.1657 unique data were used to solve (direct methods) and refine the structure to give R = 0.126 and Rw = 0.118.The six-membered ring system is in a highly folded chair conformation with the phenyl group substituents on the phosphorous atoms oriented in the equatorial positions.The dihedral angles of the P-CH2-P plane with the P4 basal plane is a remarkable 101.8 grad (avarage).This dihedral angle is the closestto perpendicular ever observed for a monocyclic ring system.
- Laneman, Scott A.,Fronczek, Frank R.,Stanley, George G.
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- Synthesis and NMR Spectral Properties of Phosphines in the 2-Phosphabicyclooct-5-ene and 2-Phosphabicycloocta-5,7-diene Systems
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1,6-Dihydrophosphorin 1-oxides were synthesized by dehydration of 3-hydroxy-1,2,3,6-tetrahydrophosphorin 1-oxides; Diels-Alder reactions with maleic acid derivatives gave the 2-phosphabicyclooct-5-ene ring system, while reaction with dimethyl acetylenedicarboxylate gave the corresponding octa-5,7-diene system.The latter system was also approached by lead tetraacetate oxidation of a dicarboxylic acid in the oct-5-ene system.Removal of the phosphoryl oxygen required very gentle conditions with the dienes to prevent fragmentation.This was accomplished with trichlorosilane at -8 to 0 deg C.The dienic phosphines were stable at 0-25 deg C but lost the P-containing bridge at 30-50 deg C.The 31P NMR shifts of all compounds were normal and resembled monocyclic phosphorin models.This ring structure, either with one or two double bonds, therefore does not cause the strong deshielding so characteristicof the related 7-phosphanorbornene system.To interpret the 1H and 13C NMR spectra of the dienic phosphines, 2-D techniques were used.
- Quin, Louis D.,Hughes, Alan N.,Kisalus, John C.,Pete, Bela
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p. 1722 - 1729
(2007/10/02)
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- Linear Oligophosphaalkanes, XIX. - Partial Alkylation of Phenylphosphane with Dihalomethanes CH2X2 (X = Cl, Br) - A Facile Synthesis of Methylenebis(phenylphosphane), HPhP-CH2-PPhH
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The reaction of PhPHNa with CH2X2 (X = Cl, Br) in tetrahydrofuran affords methylenebis(phenylphosphane), HPhP-CH2-PPhH (2), phenylphosphane, methylphenylphosphane, PhPHMe, and 1,2,3,4-tetraphenylcyclo-5-carba-1,2,3,4-tetraphosphane, CH2(PPh)4 (3).HPhP-CH2-PPhH (2) may be obtained in a facile one-step synthesis with yields up to 70percent by reaction of PhPH2 with CH2Cl2 and KOH in dimethyl sulfoxide/H2O or dimethylformamide/H2O.The formation of PhPHMe and CH2-(PPh4)4 may be explained by a reaction scheme including P-phenylphosphaalkene PhP=CH2 and HPhP-CH2Cl as reactive intermediates.The reactions between PhPHM (M = Na, K) and CH2Cl2 or CH2Br2 respectively, have been studied by independent experiments.
- Langhans, Klaus P.,Stelzer, Othmar
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p. 1707 - 1712
(2007/10/02)
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- A Simple Synthesis and Some Synthetic Applications of Substituted Phosphide and Phosphinite Anions
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Based on data for the acidity relationship of phosphines and phosphinous acids and water in dimethyl sulfoxide and water, a simple method is reported for the generation of phosphide and phosphinite anions by the action of concentrated aqueous alkali on primary and secondary phosphines as well as phosphinous acids in dimethyl sulfoxide or other dipolar aprotic solvents.Alkylation of the anion yields secondary and tertiary phosphines, polyphosphines, functionally substituted phosphines as well as similarly substituted phosphine oxides.Phosphinous acids have beenalkylated in various solvents in two-phase systems containing concentrated aqueous alkali and tetrabutylammonium iodide as phase transfer catalyst.
- Tsvetkov, E. N.,Bondarenko, N. A.,Malakhova, I. G.,Kabachnik, M. I.
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p. 198 - 208
(2007/10/02)
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