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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.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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An effective synthesis of chiral atropoisomeric biaryl phosphine-olefin compounds via palladium-catalyzed enantioselective C-H olefination has been developed for the first time. The reactions are operationally simple, tolerate wide functional groups, and have a good ee value. Notably, P(O)R2 not only acts as the directing group to direct C-H activation in order to make a useful ligand but also serves to facilitate composition of the product in a useful manner in this transformation.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A rhodium-catalyzed system is introduced for in situ modification of biaryl-type monophosphines with hydrosilanes through a PIII-chelation-assisted dehydrogenative silylation reaction. A series of ligands containing silyl groups with different steric and electronic properties were obtained with excellent regioselectivities. This method offers many advantages, including the use of commercially available phosphines, no requirement for an external ligand or oxidant, a broader substrate scope, high efficiency, and access to a single regioisomer. Based on the outstanding properties of the parent scaffolds, the silyl-substituted phosphines serve as excellent ligands in Pd-catalyzed asymmetric Suzuki coupling reactions.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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13885-09-1, Name is 2-(Diphenylphosphino)biphenyl, molecular formula is C24H19P, belongs to chiral-phosphine-ligands compound, is a common compound. In a patnet, once mentioned the new application about 13885-09-1, Quality Control of: 2-(Diphenylphosphino)biphenyl

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.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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1-Arylvinyl formates as a kind of new CO surrogate have been explored for the first time. Most of the known CO precursors usually produce undesired residuals, which have to be removed. In this strategy, after CO release, the in situ generated acetophenones from 1-arylvinyl formates can be successfully applied as a good ketone source in the synthesis of chalcones with benzaldehydes via a palladium-catalyzed reductive carbonylation reaction. A variety of chalcones were isolated in satisfactory to good yields with good substrates compatibilities under mild conditions.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Efficient, phosphine-directed ortho C?H borylation of arylphosphine derivatives was achieved using Ru catalysts for the first time. The reaction is applicable to various tertiary arylphosphine and arylphosphinite derivatives to give (o-borylaryl)phosphorus compounds in high yields. This reaction enables easy access to a variety of functionalized phosphine ligands and ambiphilic phosphine boronate compounds, thus realizing a new late-stage modification of phosphorus compounds.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Efficient bulky phosphines for the selective telomerization of 1,3-butadiene with methanol

A series of bulky phosphines containing substituted biphenyl, 2-methylnaphthyl, or 2,7-di-tert-butyl-9,9-dimethylxanthene moiety were prepared. They were used in the preparation of new monophosphine-palladium(0)- dvds complexes, which were employed as catalysts for the selective telomerization of 1,3-butadiene with methanol to obtain 1-methoxyocta-2,7-diene (1-MOD), the key intermediate in the Dow 1-octene process. Several ligands showed improved selectivity and yield compared to that of the benchmark ligand PPh3. Especially 2,7-di-tert-butyl-9,9-dimethylxanthen-4-yl- diphenylphosphine (4, “mono-xantphos”) stands out as an excellent ligand in terms of yield, selectivity, and stability.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Palladacycles incorporating a carboxylate-functionalized phosphine ligand: syntheses, characterization and their catalytic applications toward Suzuki couplings in water

A series of acetato-bridged [C^X]-type (C = aryl carbanion, X = N, P) palladacycles (1?5) of the general formula [Pd(mu-CH3COO)(C^X)]2 were synthesized as metal precursors via slightly modified procedures. However, in the case of complex 5 with Dpbp (Dpbp = 2?-(diphenylphosphino-kappaP)[1,1?-biphenyl]-2-yl-kappaC) as the supporting C^P ligand, an unexpected dinuclear complex [Pd(mu-CO2)(Dpbp)]2 (6) was obtained as a by-product and structurally determined by X-ray crystallography. The reactions of complexes 1?4 with 2-(diphenylphosphino)benzoic acid conveniently afforded four carboxylate-functionalized phosphine complexes [Pd(C^N)(Dpb)] (Dbp = 2-(diphenylphosphino-kappaP)benzoato-kappaO, 7?10), two of which (9/10) are newly synthesized in the present work and have been fully characterized. A comparative catalytic study revealed that complex [Pd(Ppy)(Dpb)] (7) (Ppy = 2-(2-pyridinyl-kappaN)phenyl-kappaC) is the best performer in Suzuki cross-couplings in H2O. In addition, complex 7 exhibits much better catalytic activity compared to the non-functionalized phosphine equivalent [Pd(OAc)(PPh3)(Ppy)] (11), which clearly indicates the superiority of incorporating a carboxylate-functionalized phosphine ligand into the palladacycles. A preliminary mechanistic study uncovered a different precatalyst initiation pathway compared to other known analogues of catalyst precursors.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Application of 13885-09-1, Chemistry can be defined as the study of matter and the changes it undergoes. You’ll sometimes hear it called the central science because it is the connection between physics and all the other sciences, starting with biology.13885-09-1, Name is 2-(Diphenylphosphino)biphenyl, molecular formula is C24H19P. In a patent, introducing its new discovery.

Highly chemoselective Mono-Suzuki arylation reactions on all three dichlorobenzene isomers and applications development

A Pd catalyst system is described that allows very high chemoselective monoarylation on all three isomers of dichlorobenzene. Direct application of these commodity chemicals to high-value ligands, anilines, azides, and carbazoles was achieved through this process discovery.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Cyclometalation in the aliphatic ring occurs in the reaction between [CoCH3(PMe3)4] and 5-(diphenylphosphanyl)-1,2,3,4-tetrahydronaphthalene to give [{8-(diphenylphosphanyl)-1,2,3,4-tetrahydronaphthyl-(C1,P)} tris(trimethylphosphane)cobalt] (1), containing a five-membered metallacycle as shown in the molecular structure. While 1-(diphenylphosphanyl)naphthalene reacts accordingly, affording [{8-(diphenylphosphanyl)naphthyl-(C1,P)}tris(trimethylphos phane)cobalt] (2), 2-(diphenylphosphanyl)biphenyl yields ortho-metalated [{2-(diphenylphosphanyl)-3-phenylphenyl-(C1,P)}tris (trimethylphosphane)cobalt] (3), containing a four-membered metallacycle. 1-(Diphenylphosphanyl)-8-methylnaphthalene is metalated in the aliphatic substituent to form [{[8-(diphenylphosphanyl)naphth-1-yl]methyl-(C,P)}tris (trimethylphosphane)cobalt] (4). The molecular structure shows a trigonal-bipyramidal configuration of the cobalt atom accommodating a six-membered metallacycle. 2-(Diphenylphosphanyl)styrene replaces two trimethylphosphane ligands to give [{2-(diphenylphosphanyl)styrene-(C,C-eta2,P)/methyl-bis (trimethylphosphane)cobalt] (5), avoiding metalation. Replacement of equatorial trimethylphosphane in compounds 1-3 by ethene gives pi-ethene complexes 6-8. In the molecular structure of 7 the C-C vector of the pi-ethene ligand is arranged in the equatorial plane of a trigonal bipyramid. Under 1 bar of CO, compound 2 forms a monocarbonyl complex 9, in which an equatorial carbonyl ligand is found in the molecular structure. Iodomethane transforms 2 into pentacoordinate [{2-(diphenylphosphanyl)naphthyl-(C1,P)/iodobis- (trimethylphosphane)cobalt] (10) with retention of the metallacycle. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate