- SYNTHESIS AND PHYSICAL PROPERTIES OF CHLORODI(o-TOLYL)PHOSPHINE, LITHIUM DI(o-TOLYL)PHOSHIDE AND THE DIPHOSPHINE SERIES (o-TOLYL)2P(CH2)NP(o-TOYLYL) (n =1-4, 6,8)
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The starting material chlorodi(o-tolyl)phosphine has been prepared by the reaction of phosphorus trichloride and the Grignard of o-chlorotoluene.The intermediate lithium di(o-tolyl)phosphide was obtained by the direct reaction of lithium metal and chlorod
- Clark, Peter W.,Mulraney, Bernard J.
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Read Online
- Palladium-Catalyzed Cascade C?O Cleavage and C?H Alkenylation of Phosphinyl Allenes: An Expeditious Approach to 3-Alkenyl Benzo[b]phosphole Oxides
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A phosphine oxide-directed intramolecular cyclization of phosphinyl allenes is established for the first time. The palladium-catalyzed intramolecular cyclization provides an unprecedented cascade C?O cleavage and direct C?H alkenylation toward novel 3-alk
- Liu, Teng,Sun, Xue,Wu, Lei
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supporting information
p. 2005 - 2012
(2018/03/27)
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- Method for preparing diarylphosphoryl chloride compound
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The invention discloses a method for preparing a diarylphosphochlorine compound and belongs to the field of organic synthesis. The method is as follows: the diarylphosphochlorine compound is preparedby reaction of triarylphosphine as a starting material with phosphorus trichloride in the presence of zinc trifluoromethanesulfonate as a catalyst and distillation. Compared with the prior art, the method has the advantages of high reaction yield and simple post-treatment, is particularly suitable for preparation of the diarylphosphochlorine compound with a substituent, and is more suitable for industrial production. The obtained diarylphosphochlorine compound can be used as a ligand for synthesizing metal catalysts, and is applied to the fields such as organic photoelectric materials and medicines.
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Paragraph 0016-0017
(2018/06/15)
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- Diastereoselective desymmetrization of diarylphosphinous acid-borane amides under Birch reduction
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Treatment of diarylphosphinous acid-borane amides possessing chiral amido functionality with an alkali metal solution in liquid ammonia induced a preferential dearomatization of one aryl substituent at phosphorus leading to the formation of non-equimolar amounts of diastereomers. Diastereoselectivity of dearomatization depends strongly on the structure of a chiral auxiliary.
- Stankevi?, Marek
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p. 6082 - 6102
(2015/06/08)
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- TETRAMERISATION OF ETHYLENE
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A process for the tetramerisation of ethylene includes contacting ethylene with a catalyst under ethylene oligomerisation conditions. The catalyst comprises a source of chromium, a ligating compound, and an activator. The ligating compound includes a phosphine that forms part of a cyclic structure.
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- Palladium-catalyzed allylic alkylation of carboxylic acid derivatives: N-acyloxazolinones as ester enolate equivalents
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Triple A: A general asymmetric allylic alkylation of ester enolate equivalents at the carboxylic acid oxidation state is reported. N-Acylbenzoxazolinone-derived enol carbonates were synthesized and employed in the palladium-catalyzed alkylation reaction. The imide products were readily converted into a series of carboxylic acid derivatives without loss of enantiopurity.
- Trost, Barry M.,Michaelis, David J.,Charpentier, Julie,Xu, Jiayi
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supporting information; experimental part
p. 204 - 208
(2012/02/16)
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- Ligand effects in chromium diphosphine catalysed olefin co-trimerisation and diene trimerisation
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A series of symmetric and unsymmetric N,N-bis(diarylphosphino)amine ('PNP') ligands (Ar2PN(R)PNAr′2: R = Me, Ar2 = o-anisyl, Ar′2 = Ph, 1, R = Me, Ar2 = o-tolyl, Ar′2 = Ph, 2, R = Me, Ar2 = Ph(o-ethyl), Ar′2 = Ph, 3, R = Me, Ar2 = Ar′2 = o-anisyl, 4, R = iPr, Ar2 = Ar′2 = Ph, 5) and symmetric N,N′-bis(diarylphosphino)dimethylhydrazine ('PNNP') ligands (Ar2PN(Me)N(Me)PAr2: Ar2 = o-tolyl, 6, Ar 2 = o-anisyl, 7) have been synthesised. Catalytic screening for ethene/styrene co-trimerisation and isoprene trimerisation was performed via the in situ complexation to [CrCl3(THF)3] followed by activation with methylaluminoxane (MAO). PNNP catalytic systems showed a significant increase in activity and selectivity over previously reported PNP systems in isoprene trimerisation. Comparing the symmetric and unsymmetric variants in ethene and styrene co-trimerisation resulted in a switch in selectivity, an unsymmetric catalytic (o-anisyl)2PN(Me)PPh 2 (1) ligand system affording unique incorporation of two styrenic monomers into the co-trimer product distribution differing from the familiar two ethene and one styrene ω-substituted alkenes. Complexes of the type [(diphosphine)Cr(CO)4] 8-11 were also synthesised, the single-crystal X-ray diffraction of which are reported. We propose the mechanisms of these catalytic transformations and an insight into the effect of the ligand series on the chromacyclic catalytic intermediates. The Royal Society of Chemistry.
- Bowen, Lucy E.,Charernsuk, Manutsavin,Hey, Thomas W.,McMullin, Claire L.,Orpen, A. Guy,Wass, Duncan F.
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experimental part
p. 560 - 567
(2010/04/03)
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- POLYMERISATION PROCESS CATALYSED BY A BIDENTATE BISPHOSPHINE-GROUP VIII METAL COMPLEX
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A process for the polymerization and copolymerization of olefins is disclosed, comprising contacting the monomeric olefin under polymerization conditions with a polymerization catalyst or catalyst system which comprises (a) a source of a Group VIII metal; (b) a bidentate phosphine ligand having the formula (R1)(R1)P-X-P(R1)(R1), where each R1 is independently selected from a phenyl group or a substitued phenyl group with the proviso that at least one of the R1 groups is a phenyl group having at least one ortho substituent, and X is a bridging group of the structure -[N]x-[P]y-[N]- where x and y are independently 0 or 1, or -C(R4)2- where R4 may be the same or different and is hydrogen or a monovavlent hydrocarbyl, substituted hydrocarbyl or hetero-hydrocarbyl group; and optionally (c) a promoter.
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Page/Page column 10
(2010/11/27)
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- Development of efficient and reusable diarylphosphinopolystyrene-supported palladium catalysts for C-C bond forming cross-coupling reactions
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Short and versatile syntheses of reusable diarylphosphinopolystyrene- supported palladium catalysts 3a-j are described. The bis(o-tolyl)phosphino catalyst 3b is particularly efficient for the Suzuki and Sonogashira cross-couplings, whereas the bis(m-tolyl)phosphino catalyst 3c is the most active catalyst for Heck reactions. The couplings are performed under non-anhydrous reaction conditions and require only low amounts of supported palladium (0.5 mequivs. for Suzuki-Miyaura, 1.0 mequiv. for Sonogashira and 0.5 mequivs. for Heck reactions could be sufficient). Catalysts 3a-j are recovered by filtration and can be reused more than four times with no loss of efficiency.
- Schweizer, Stephane,Becht, Jean-Michel,Le Drian, Claude
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p. 1150 - 1158
(2008/03/28)
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- Assembly of hydrophobic shells and shields around lanthanides
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Luminescent lanthanide complexes have been developed, based on the assembly of bulky ligands around the lanthanide ion, to provide shell-type protection of the ion from coordinated solvent molecules. Aryl-functionalised imidodiphosphinate ligands (tpip an
- Magennis, Steven W.,Parsons, Simon,Pikramenou, Zoe
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p. 5761 - 5771
(2007/10/03)
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- Effect of fluorine and trifluoromethyl substitution on the donor properties and stereodynamical behaviour of triarylphosphines
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A series of 2-, 3- or 4-trifluoromethyl substituted triarylphosphines and their oxide, chalcogenide and Fe(CO)4 derivatives have been prepared and characterised spectroscopically and crystallographically. Electronic effects of CF3 su
- Howell, James A. S.,Fey, Natalie,Lovatt, Jonathan D.,Yates, Paul C.,McArdle, Patrick,Cunningham, Desmond,Sadeh, Einat,Gottlieb, Hugo E.,Goldschmidt, Zeev,Hursthouse, Michael B.,Light, Mark E.
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p. 3015 - 3028
(2007/10/03)
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- Ligand Electronic Effects in Asymmetric Catalysis: Enhanced Enantioselectivity in the Asymmetric Hydrocyanation of Vinylarenes
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The enantioselectivity of the nickel-catalyzed, asymmetric hydrocyanation of vinylarenes using glucosederived, chiral phosphinite ligands, L, increases dramatically when the ligands contain electron-withdrawing P-aryl substituents.The substrate and solvent also strongly influence the enantioselectivity, with the highest ee's (85-91percent for 6-methoxy-2-vinylnaphthalene (MVN)) obtained for the hydrocyanation of electron-rich vinylarenes in a nonpolar solvent such as hexane.Mechanistic studies suggest the catalytic cycle consists of an initial HCN oxidative addition or vinylarene coordination to "NiL", followed by insertion to form an (η3-benzyl)nickel cyanide complex, and irreversible reductive elimination of the nitrile.A kinetic analysis of the NiLa(COD) (La, P-aryl=3,5-(CF3)2C6H3) catalyzed hydrocyanation of MVN indicates that as the HCN concentration is increased the catalyst resting state shifts from NiLa(COD) to a complex containing both MVN and HCN, presumably the (η3-benzyl)nickel cyanide intermediate NiLa(η3-CH3CHC10H6OCH3)CN.A 31P NMR analysis of the intermediate NiLa(MVN) shows little ground state differentiation of the MVN enantiofaces and suggests that the enantioselectivity is determined later in the mechanism.Deuterium labeling studies suggest that electron-withdrawing P-aryl substituents increase the rate of reductive elimination of the product nitrile from the (η3-benzyl)nickel cyanide intermediate and, on this basis, a rationale for the ligand electronic effect is proposed.
- Casalnuovo, Albert L.,RajanBabu, T. V.,Ayers, Timothy A.,Warren, Timothy H.
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p. 9869 - 9882
(2007/10/02)
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- Hydrolysis of Diarylphosphinic Amides in Acidic Solution: Steric Inhibition and Mechanism
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The pseudo-first-order rate constants for the hydrolysis of diphenylphosphinic amide Ph2P(O)NH2 and its di-p-tolyl, di-o-tolyl, and dimesityl analogues (106kψ 3 630, 2 340, 81.0, and 3.27 s-1 respectively with H(1+) 0.0662M and T 30.2 deg C) in water-dioxan (9:1 v/v) containing perchloric acid show that reaction is sterically hindered by ortho-methyl substituents in the P-aryl groups.Steric inhibition is as great, or greater, in the hydrolysis of the corresponding (N-phenyl)diarylphosphinic amides (106kψ 5 440, 4 470, 54.9 and 0.88 s-1 respectively with H(1+) 1.36M and T 39.9 deg C) and (N-p-nitrophenyldiarylphosphinic amides (106kψ 724, 702, 6.57, and 0.098 s-1 respectively with H(1+) 2.58M and T 39.9 deg C) even though the departing amine is less nucleophilic.Such sensitivity to steric hindrance is consistent with associative (A2) mechanism for the hydrolysis of all the substrates.
- Harger, Martin J. P.
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p. 154 - 160
(2007/10/02)
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