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Synthesis of stable phosphomide ligands and their use in Ru-catalyzed hydrogenations of bicarbonate and related substrates

New benzoyl- and naphthoyl-substituted phosphines have been synthesized, which are stable to air and moisture. Testing these so-called phosphomide ligands in the presence of different ruthenium precursors, the hydrogenation of sodium bicarbonate (NaHCO3) to sodium formate (NaHCO2) proceeded with good catalyst turnover numbers in the range of 1300-1600 at 80 C and a total pressure of hydrogen of 60 bar in the absence of amines or other additives. Similarly, catalytic hydrogenations of carbon dioxide, cinnam-, and benzaldehyde were possible with these new ruthenium complexes. As an intermediate of the catalytic cycle the defined ruthenium complex [(eta6-C6H6)-RuCl2(Cy 2P(1-naphthoyl)] (Cy=cyclohexyl) was prepared and characterized by X-ray crystallography. Ruthenium and phosphor work wonders: Air-stable ruthenium phosphomide complexes are active catalysts in the hydrogenation of sodium bicarbonate, carbon dioxide, and carbonyl compounds. Hydrogenation proceeds with high catalyst turnover numbers in the absence of amines or other additives. The application range of these new ruthenium catalysts also includes the hydrogenation of cinnamaldehyde and benzaldehyde. Copyright

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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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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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Expedient copper-free one-pot alkynylation-cyclization sequence for the preparation of 2-substituted 7-azaindoles

Abstract 2-Substituted 7-azaindoles are rapidly and efficiently prepared in a one-pot copper-free alkynylation-cyclization sequence starting from 2-aminopyridyl halides and terminal alkynes. Most importantly the amino nitrogen atom neither requires activation nor protection throughout the sequence.

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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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Chiral Bifunctional Phosphine Ligand Enabling Gold-Catalyzed Asymmetric Isomerization of Alkyne to Allene and Asymmetric Synthesis of 2,5-Dihydrofuran

The asymmetric isomerization of alkyne to allene is the most efficient and the completely atom-economic approach to this class of versatile axial chiral structure. However, the state-of-the-art is limited to tert-butyl alk-3-ynoate substrates that possess requisite acidic propargylic C-H bonds. Reported here is a strategy based on gold catalysis that is enabled by a designed chiral bifunctional biphenyl-2-ylphosphine ligand. It permits isomerization of alkynes with nonacidic alpha-C-H bonds and hence offers a much-needed general solution. With chiral propargylic alcohols as substrates, 2,5-disubstituted 2,5-dihydrofurans are formed in one step in typically good yields and with good to excellent diastereoselectivities. With achiral substrates, 2,5-dihydrofurans are formed with good to excellent enantiomeric excesses. A novel center-chirality approach is developed to achieve a stereocontrol effect similar to an axial chirality in the designed chiral ligand. The mechanistic studies established that the precatalyst axial epimers are all converted into the catalytically active cationic gold catalyst owing to the fluxional axis of the latter.

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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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Synthesis of 4-sulfonatobenzylphosphines and their application in aqueous-phase palladium-catalyzed cross-coupling

Aqueous-biphasic catalysis offers the potential for safer and more environmentally sustainable synthetic processes. In addition, hydrophilic supporting ligands allow homogeneous catalysts to be readily separated from organic products and potentially reused. The synthesis of two new water-soluble ligand precursors, di-tert-butyl(4-sulfonatobenzyl)phosphonium and di-1-adamantyl(4-sulfonatobenzyl)phosphonium, are reported. The air-stable, zwitterionic phosphonium salts were prepared by the reaction of dialkylphosphines with ethyl 4-bromomethylbenzenesulfonate, which results in a one-pot alkylation followed by deprotection of the ethyl sulfonate. This methodology provides an operationally simpler route to sulfonated benzylphosphines than electrophilic sulfonation. The new phosphine ligands were applied to aqueous-phase Suzuki and Sonogashira couplings of aryl bromides.

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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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DI-1-ADAMANTYLPHOSPHIN, EIN SRERISCH HOCH GEHINDERTES SEKUNDAERES PHOSPHIN. DARSTELLUNG UND REAKTIONEN

Di-1-adamantylphosphine 1 was synthesized by reduction of (1-Ad)2P(:O)Cl with LiAlH4 or HSiCl3.The reaction of 1 with H2O2, elemental sulfur and selenium afforded the corresponding secondary phosphine oxides, sulfides and selenides, (1-Ad)2P(:X)H (X = O, S, Se).In the reaction of 1 with two equivalents of Me3SiN3 oxidation occured with formation of (1-Ad)2P(:NSiMe3)NHSiMe3 6.Despite the steric hindrance, MeI quaternized the P-atom in 1 to give <(1-Ad)2PHMe>I 7.The phosphine (1-Ad)2PMe 8 was formed in the reaction of 7 with NEt3 and was oxidized by O2 to give (1-Ad)2P(:O)-Me 9.Key words: Di-1-adamantylphosphine; Di-1-adamantylphosphine oxide, sulfide, selenide, NMR.

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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 highly versatile catalyst system for the cross-coupling of aryl chlorides and Amines

The syntheses of 2-(di-tertbutylphosphino)-N,N-dimethylaniline (L1, 71%) and 2-(di-1-adamantylphosphino)-N,N-dimethylaniline (L2, 74%), and their application in BuchwaldHartwig amination, are reported. In combination with [Pd(allyl)Cl]2 or [Pd(cinnamyl)Cl]2, these structurally simple and air-stable P,N ligands enable the cross-coupling of aryl and heteroaryl chlorides, including those bearing as substituents enolizable ketones, ethers, esters, carboxylic acids, phenols, alcohols, olefins, amides, and halogens, to a diverse range of amine and related substrates that includes primary alkyl- and arylamines, cyclic and acyclic secondary amines, N-H imines, hydrazones, lithium amide, and ammonia. In many cases, the reactions can be performed at low catalyst loadings (0.5-0.02 mol % Pd) with excellent functional group tolerance and chemoselectivity. Examples of cross-coupling reactions involving 1,4-bromochlorobenzene and iodobenzene are also reported. Under similar conditions, inferior catalytic performance was achieved when using Pd(OAc)2, PdCl2, [PdCl2(cod)] (cod = 1,5-cyclooctadiene), [PdCl 2(MeCN)2], or [Pd2(dba)3] (dba = dibenzylideneacetone) in combination with L1 or L2, or by use of [Pd(allyl)Cl]2 or [Pd(cinnamyl)Cl]2 with variants of L1 and L2 bearing less basic or less sterically demanding substituents on phosphorus or lacking an ortto-dimethylamino fragment. Given current limitations associated with established ligand classes with regard to maintaining high activity across the diverse possible range of C-N coupling applications, L1 and L2 represent unusually versatile ligand systems for the cross-coupling of aryl chlorides and amines

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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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TRANSITION METAL ISONITRILE CATALYSTS

The present disclosure relates to new transition metal isonitrile compounds, processes for the production of the compounds and the use of the compounds as catalysts. The disclosure also relates to the use of the metal isonitrile compounds as catalysts for hydrogenation and transfer hydrogenation of compounds containing one or more carbon-oxygen, and/or carbon-nitrogen and/or carbon-carbon double bonds.

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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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General synthesis and catalytic applications of di(1-adamantyl) alkylphosphines and their phosphonium salts

An improved synthesis of di(1-adamantyl)alkylphosphines by alkylation of di(1-adamantyl)phosphine followed by deprotonation of the resulting phosphonium halide is described. Compared to previous protocols for the synthesis of this class of compounds, the procedure does not require chlorination of the secondary phosphine by phosgene, or formation of sensitive lithium di(1-adamantyl) phosphide. Selected examples of the prepared phosphonium salts and phosphines are shown to be excellent ligands for the palladium-catalyzed cross-coupling reaction of chloroarenes with arylboronic acids.

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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