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New phosphine-functionalized NHC ligands: Discovery of an effective catalyst for the room-temperature amination of aryl chlorides with primary and secondary amines

We report convenient and high-yielding syntheses of new phosphine-functionalized dihydroimidazolium salts and demonstrate their utility as ligand precursors for Buchwald-Hartwig amination. Several examples of the general formula [1-Mes-3-{2-(PR2)phenyl}imidazolidin-2-ylium][BF 4] have been prepared, where phosphines of varying steric and electronic properties (R = Ph (9), Cy (10), 1-Ad (11)) are tethered by an o-phenylene group. The synthesis was not adaptable to N-aryl groups other than mesityl, giving unexpected phosphonium salt species instead. The synthesis was adapted to flexible benzyl-linked variants of the formula [1-Ar-3-{2-(PCy 2)benzyl}imidazolidin-2-ylium][BF4], which allowed more steric variation of the dihydroimidazolium N-aryl group (Ar = Mes (21), Dipp (22)). A preliminary study of these hybrid NHC/P ligands in Buchwald-Hartwig amination catalysis (in situ precatalyst formation) revealed 11 to be the most active of the series. Premixing the isolated free NHC ligand 1-Mes-3-{2-(PAd2)phenyl}imidazolidin-2-ylidene (23) with [Pd(cinnamyl)Cl]2 provided a highly active precatalyst that performed well at room temperature and 1 mol % catalyst loading. The system was shown to have an unprecedented ability to arylate both primary alkylamines (monoarylation) and secondary dialkylamines with aryl chlorides at room temperature. Electron-rich and -poor aryl and heteroaryl halides, as well as those featuring ortho substitution, were well tolerated, while substrates featuring both primary and secondary amine groups were selectively arylated at the NH2 position. Furthermore, a preliminary examination of performance in ammonia arylation and acetone alpha-arylation showed promising results, giving good conversion and high selectivity for monoarylation in both cases.

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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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Reference of 1608-26-0, Catalysts are substances that increase the reaction rate of a chemical reaction without being consumed in the process. 1608-26-0, Name is Tris(dimethylamino)phosphine
, molecular formula is P[N(CH3)2]3. In a Article£¬once mentioned of 1608-26-0

Highly selective markovnikov addition of hypervalent H-spirophosphoranes to alkynes mediated by palladium acetate: Generality and mechanism

Palladium acetate efficiently catalyzes the addition of an H-spirophosphorane (pinacolato)2PH to alkynes to give Markovnikov addition products highlyselectively. The addition products can be easily converted to the corresponding alkenylphosphonates and phosphonicacids viasimple hydrolysis or thermal decomposition. This new reaction isa general method for the introduction of phosphorus functionality to the internal carbons of terminal alkynes, resolving the problem of the regioselectivity associated with hydrophosphorylation reactions so far reported. Mechanistic studies confirmed that (a) palladium acetate was reduced to metallic palladium by H-spirophosphorane, (b) the P-H bond of H-spirophosphorane could be activated by zero-valent platinum complexes to give the corresponding hydridoplatinum complexes, and (c) an alkenylpalladium species was identified from the reaction of palladium acetate with H- spirophosphorane and diphenylacetylene. These results support a reaction mechanism that palladium acetate was first reduced by H-spirophosphorane to give zero-valent palladium. This zero-valent palladium might insert into the P-H bond of the H-spirophosphorane to give a hydridopalladium species which then added to alkyne via the addition of H-Pd bond to form an alkenylpalladium species with the hydrogen atom added to the terminal carbon of alkynes. Reductive elimination of the alkenylpalladium affords the addition product.

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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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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.224311-51-7, Name is 2-(Di-tert-Butylphosphino)biphenyl, molecular formula is C20H27P. In a Article£¬once mentioned of 224311-51-7, COA of Formula: C20H27P

Dinuclear PdI Catalysts in Equilibrium Isomerizations: Mechanistic Understanding, in Silico Casting, and Catalyst Development

The unique reactivity profile of the dinuclear PdI complex [PdI(mu-Br)tBu3P]2 as an isomerization cocatalyst has enabled orthogonal tandem processes ranging from styrene syntheses to biodiesel refining. We have now elucidated the mechanistic basis of its distinct catalytic profile by density functional theory calculations and experimental studies. Activation of the catalyst proceeds intramolecularly, giving rise to a dinuclear complex composed of a reactive palladium hydride and an inert palladacycle. This complex mediates double bond migrations with an energy span of 9.5 kcal/mol, which is well below those calculated for known catalysts. Its dissociation leads to an even more active monophosphinopalladium hydride catalyst and an inert dinuclear bispalladacycle. In the main deactivation pathway, two mononuclear Pd species react with each other, liberating a hydrogenation product and regenerating the catalyst precursor [PdI(mu-Br)tBu3P]2. The experimentally observed buildup of dinuclear palladacycles during the catalysis is, thus, the result of conversion of a binuclear into mononuclear Pd-H catalyst. Phosphines, which would deactivate metathesis cocatalysts, are not liberated at any stage. This explains the unique suitability of [PdI(mu-Br)tBu3P]2 for isomerizing metatheses. The mechanistic insights were used for the in silico casting of a catalyst generation, targeting complexes with a reduced barrier toward the formation of dinuclear Pd-H species, a low energy span of the catalytic cycles, and increased barriers either toward deactivation or, alternatively, toward dissociation to short-lived mononuclear complexes. Complexes with bisadamantyl-n-butylphosphine ligands were identified as lead structures. Experimental studies with model catalysts confirmed the validity of the predicted structure-activity relationship.

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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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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.166330-10-5, Name is (Oxybis(2,1-phenylene))bis(diphenylphosphine), molecular formula is C36H28OP2. In a Review£¬once mentioned of 166330-10-5, Formula: C36H28OP2

Valorization of biomass derived terpene compounds by catalytic amination

This review fills an apparent gap existing in the literature by providing an overview of the readily available terpenes and existing catalytic protocols for preparation of terpene-derived amines. To address the role of solid catalysts in amination of terpenes the same reactions with homogeneous counterparts are also discussed. Such catalysts can be considered as a benchmark, which solid catalysts should match. Although catalytic systems based on transition metal complexes have been developed for synthesis of amines to a larger extent, there is an apparent need to reduce the production costs. Subsequently, homogenous systems based on cheaper metals operating by nucleophilic substitution (e.g., Ni, Co, Cu, Fe) with a possibility of easy recycling, as well as metal nanoparticles (e.g., Pd, Au) supported on amphoteric oxides should be developed. These catalysts will allow synthesis of amine derivatives of terpenes which have a broad range of applications as specialty chemicals (e.g., pesticides, surfactants, etc.) and pharmaceuticals. The review will be useful in selection and design of appropriate solid materials with tailored properties as efficient catalysts for amination of terpenes.

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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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Formation of gold(III) alkyls from gold alkoxide complexes

The gold(III) methoxide complex (C^N^C)AuOMe (1) reacts with tris(p-tolyl)phosphine in benzene at room temperature under O abstraction to give the methylgold product (C^N^C)AuMe (2) together with O=P(p-tol)3 ((C^N^C) = [2,6-(C6H3 tBu-4)2pyridine]2-). Calculations show that this reaction is energetically favorable (DeltaG = -32.3 kcal mol-1). The side products in this reaction, the Au(II) complex [Au(C^N^C)]2 (3) and the phosphorane (p-tol)3P(OMe)2, suggest that at least two reaction pathways may operate, including one involving (C^N^C)Au? radicals. Attempts to model the reaction by DFT methods showed that PPh3 can approach 1 to give a near-linear Au-O-P arrangement, without phosphine coordination to gold. The analogous reaction of (C^N^C)AuOEt, on the other hand, gives exclusively a mixture of 3 and (p-tol)3P(OEt)2. Whereas the reaction of (C^N^C)AuOR (R = But, p-C6H4F) with P(p-tol)3 proceeds over a period of hours, compounds with R = CH2CF3, CH(CF3)2 react almost instantaneously, to give 3 and O=P(p-tol)3. In chlorinated solvents, treatment of the alkoxides (C^N^C)AuOR with phosphines generates [(C^N^C)Au(PR3)]Cl, via Cl abstraction from the solvent. Attempts to extend the synthesis of gold(III) alkoxides to allyl alcohols were unsuccessful; the reaction of (C^N^C)AuOH with an excess of CH2=CHCH2OH in toluene led instead to allyl alcohol isomerization to give a mixture of gold alkyls, (C^N^C)AuR? (R? = -CH2CH2CHO (10), -CH2CH(CH2OH)OCH2CH=CH2 (11)), while 2-methallyl alcohol affords R? = CH2CH(Me)CHO (12). The crystal structure of 11 was determined. The formation of Au-C instead of the expected Au-O products is in line with the trend in metal-ligand bond dissociation energies for Au(III): M-H > M-C > M-O.

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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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Fluorous-Phase Approach to alpha-Hydroxytropolone Synthesis

alpha-Hydroxytropolones (alphaHTs) are troponoids that demonstrate inhibition against an array of therapeutically significant targets, making them potential drug leads for several human diseases. We have utilized a recently discovered one-pot three-component oxidopyrylium cycloaddition in a solid-supported synthesis of alphaHTs. Though the procedure is time efficient and generates assay-ready molecules, the system suffers from low yields and an inability to perform reaction modifications on resin-bound intermediates. In order to combat these issues with the solid-phase platform, we incorporated fluorous tags into our synthetic route. Through the implementation of fluorous phase chemistry, we demonstrate a substantial increase in the overall yield of alphaHTs, as well as an ability to execute metal-catalyzed cross coupling and amide coupling on fluorous tagged intermediates. We also show that tagged molecules can be separated from nonfluorous impurities, and vice versa, by utilizing fluorous liquid-liquid and solid-phase extractions. Hence, these proof-of-principle investigations describe the viability of a fluorous phase approach to alphaHT synthesis and its potential to serve as a combinatorial technique to produce structurally diverse substrates.

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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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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 166330-10-5, Name is (Oxybis(2,1-phenylene))bis(diphenylphosphine), molecular formula is C36H28OP2. In a Patent£¬once mentioned of 166330-10-5, Quality Control of: (Oxybis(2,1-phenylene))bis(diphenylphosphine)

NOVEL TRANSITION METAL COMPLEX AND PROCESS FOR PRODUCING OPTICALLY ACTIVE ALCOHOL WITH THE COMPLEX

A novel transition metal complex, preferably a ruthenium-phosphine complex or rhodium-phosphine complex, which is effectively usable in various asymmetric syntheses and, in particular, is more effectively usable in the asymmetric hydrogenation of various ketones; and a novel process for producing an optically active alcohol with the complex. The novel transition metal complex includes a ligand obtained by introducing a diarylphosphino group into each of the 2- and 2′-positions of diphenyl ether, benzophenone, benzhydrol, or the like. It preferably further includes an optically active 1,2-diphenylethylenediamine coordinated thereto. The complex preferably is a novel diphosphine-ruthenium-optically active diamine complex or diphosphine-rhodium-optically active diamine complex. The process comprises using the complex as an asymmetric hydrogenation catalyst to conduct the asymmetric hydrogenation of a ketone compound to thereby obtain an optically active alcohol in a high optical purity and a high yield.

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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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Blue-light emission of Cu(I) complexes and singlet harvesting

Strongly luminescent neutral copper(I) complexes of the type Cu(pop)(NN), with pop = bis(2-(diphenylphosphanyl)phenyl)ether and NN = bis(pyrazol-1-yl) borohydrate (pz2BH2), tetrakis(pyrazol-1-yl)borate (pz4B), or bis(pyrazol-1-yl)-biphenyl-borate (pz2Bph 2), are readily accessible in reactions of Cu(acetonitrile) 4+ with equimolar amounts of the pop and NN ligands at ambient temperature. All products were characterized by means of single crystal X-ray diffractometry. The compounds exhibit very strong blue/white luminescence with emission quantum yields of up to 90%. Investigations of spectroscopic properties and the emission decay behavior in the temperature range between 1.6 K and ambient temperature allow us to assign the emitting electronic states. Below 100 K, the emission decay times are in the order of many hundreds of microseconds. Therefore, it is concluded that the emission stems from the lowest triplet state. This state is assigned to a metal-to-ligand charge-transfer state (3MLCT) involving Cu-3d and pop-pi* orbitals. With temperature increase, the emission decay time is drastically reduced to e.g. to 13 s (Cu(pop)(pz2Bph2)) at ambient temperature. At this temperature, the complexes exhibit high emission quantum yields, as neat material or doped into poly(methyl methacrylate) (PMMA). This behavior is assigned to an efficient thermal population of a singlet state (being classified as 1MLCT), which lies only 800 to 1300 cm-1 above the triplet state, depending on the individual complex. Thus, the resulting emission at ambient temperature largely represents a fluorescence. For applications in OLEDs and LEECs, for example, this type of thermally activated delayed fluorescence (TADF) creates a new mechanism that allows to harvest both singlet and triplet excitons (excitations) in the lowest singlet state. This effect of singlet harvesting leads to drastically higher radiative rates than obtainable for emissions from triplet states of Cu(I) complexes.

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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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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 4020-99-9, Name is Methoxydiphenylphosphine, molecular formula is C13H13OP. In a Article£¬once mentioned of 4020-99-9, SDS of cas: 4020-99-9

Synthesis of Dialkyl 3-(Dialkylphosphinyloxy)-2-alkenephosphonate and Diphenyl-<3-(diphenylphosphinyloxy)-2-propenyl>phosphine Oxide

Dialkyl 3-(dialkoxyphosphinyloxy)-2-alkenephosphonates and diphenyl-<3-(diphenylphosphinyloxy)-2-propenyl>phosphine oxide were prepared by the reaction of the mixed reagent of trivalent phosphorus oxo acid ester and pentavalent phosphorus oxo acid chloride with several alpha,beta-unsaturated aldehyde.

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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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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.224311-51-7, Name is 2-(Di-tert-Butylphosphino)biphenyl, molecular formula is C20H27P. In a Review£¬once mentioned of 224311-51-7, Recommanded Product: 224311-51-7

N-heterocyclic carbene complexes of copper, nickel, and cobalt

The emergence of N-heterocyclic carbenes as ligands across the Periodic Table had an impact on various aspects of the coordination, organometallic, and catalytic chemistry of the 3d metals, including Cu, Ni, and Co, both from the fundamental viewpoint but also in applications, including catalysis, photophysics, bioorganometallic chemistry, materials, etc. In this review, the emergence, development, and state of the art in these three areas are described in detail.

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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