Category: 277306-29-3

Lautens, Mark; Fagnou, Keith; Rovis, Tomislav published the artcile< Rhodium-Catalyzed Asymmetric Alcoholysis and Aminolysis of Oxabenzonorbornadiene: A New Enantioselective Carbon-Heteroatom Bond Forming Process>, Name: (2S)-1-[(1S)-1-[Bis(1,1-dimethylethyl)phosphino]ethyl]-2-(diphenylphosphino)ferrocene, the main research area is oxabenzonorbornadiene rhodium catalyzed stereoselective ring opening; alcoholysis stereoselective rhodium catalyzed oxabenzonorbornadiene; aminolysis stereoselective rhodium catalyzed oxabenzonorbornadiene; naphthalenol stereoselective preparation; aminonaphthalenol stereoselective preparation.

The Rh-catalyzed asym. ring-opening of oxabenzonorbornadienes with alcs. and N nucleophiles produced trans-2-alkoxy- and amino-1,2-dihydro-1-naphthols in good yield and ≤99% ee. The effects of substituents on the aromatic ring were investigated.

Journal of the American Chemical Society published new progress about Alcoholysis (stereoselective). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Name: (2S)-1-[(1S)-1-[Bis(1,1-dimethylethyl)phosphino]ethyl]-2-(diphenylphosphino)ferrocene.

Referemce:
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

Lipshutz, Bruce H.; Amorelli, Benjamin; Unger, John B. published the artcile< CuH-Catalyzed Enantioselective Intramolecular Reductive Aldol Reactions Generating Three New Contiguous Asymmetric Stereocenters>, Recommanded Product: (2S)-1-[(1S)-1-[Bis(1,1-dimethylethyl)phosphino]ethyl]-2-(diphenylphosphino)ferrocene, the main research area is unsaturated ketone copper enantioselective intramol reductive aldol chiral phosphine; cycloalkanol stereoselective preparation; enantioselective intramol reductive aldol catalyst copper chiral phosphine.

Treatment of β,β-disubstituted-α,β-unsaturated ketones, e.g., I, bearing a ketone residue with in situ generated, catalytic CuH ligated by a nonracemic ligand leads to cycloalkanols, e.g., II, with three newly created adjacent chiral centers. Excellent de’s and ee’s are obtained for several examples studied.

Journal of the American Chemical Society published new progress about Aldol condensation catalysts, stereoselective (intramol.). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Recommanded Product: (2S)-1-[(1S)-1-[Bis(1,1-dimethylethyl)phosphino]ethyl]-2-(diphenylphosphino)ferrocene.

Referemce:
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

Lipshutz, Bruce H.; Lee, Ching-Tien; Taft, Benjamin R. published the artcile< A conjugate reduction pathway to chiral silanes using CuH>, Product Details of C32H40FeP2, the main research area is ester carboxylic silylated chiral preparation asym reduction hydrosilylation enoate; copper hydride ferrocenylphosphine catalyst asym reduction hydrosilylation enoate; silane carboxyalkyl chiral preparation asym reduction silyl enoate.

Asym. reduction of β-silyl α,β-unsaturated esters was achieved by CuH/(R,S)-PPF-P(tBu)2 reagent, affording chiral β-silylated arylalkanoate esters. β-Silyl enoates (Z)- and (E)-PhMe2SiCR:CHCO2R1 [(Z)-2, (E)-2, resp.] were prepared by Peterson or Horner-Wadsworth-Emmons olefination, resp., of the corresponding acylsilanes PhMe2SiCOR. The compounds 2 were reduced by CuH-catalyzed conjugate hydrosilylation by polymethylhydrosiloxane in the presence of chiral ferrocenylphosphine, (R,S)-1-[1-(di-tert-butylphosphino)ethyl]-2-diphenylphosphinoferrocene (1). Exptl. details concerning asym. 1,4-reduction of β-silylated-β,β-disubstituted enoates catalyzed by CuH are described.

Synthesis published new progress about Esters, α,β-unsaturated Role: RCT (Reactant), SPN (Synthetic Preparation), RACT (Reactant or Reagent), PREP (Preparation). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Product Details of C32H40FeP2.

Referemce:
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

Yen, Andy; Pham, Anh Hoang; Larin, Egor M.; Lautens, Mark published the artcile< Rhodium-Catalyzed Enantioselective Synthesis of Oxazinones via an Asymmetric Ring Opening-Lactonization Cascade of Oxabicyclic Alkenes>, Recommanded Product: (2S)-1-[(1S)-1-[Bis(1,1-dimethylethyl)phosphino]ethyl]-2-(diphenylphosphino)ferrocene, the main research area is oxabicyclic alkene amino acid ester rhodium ring opening lactonization; oxazinone stereoselective preparation.

The rhodium-catalyzed asym. ring opening reaction of oxabicyclic alkenes is shown to be an efficient method for synthesizing chiral heterocycles. We demonstrate that the pairwise combination of chiral catalyst with chiral amino-acid-derived pronucleophiles results in a stereodivergent synthesis of diastereomeric hydroxyesters. A favorable conformational preference induces the subsequent lactonization of one diastereomer leading to the highly enantioselective synthesis of oxazinones.

Organic Letters published new progress about Alkenes Role: RCT (Reactant), RACT (Reactant or Reagent) (Oxabicyclic). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Recommanded Product: (2S)-1-[(1S)-1-[Bis(1,1-dimethylethyl)phosphino]ethyl]-2-(diphenylphosphino)ferrocene.

Referemce:
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

Roy, Amy H.; Hartwig, John F. published the artcile< Oxidative Addition of Aryl Tosylates to Palladium(0) and Coupling of Unactivated Aryl Tosylates at Room Temperature>, Application of C32H40FeP2, the main research area is palladium oxidative addition phenyl tosylate mechanism kinetics; crystal structure palladium phenyl bromo ferrocene diphosphine chelate preparation; mol structure palladium phenyl bromo ferrocene diphosphine chelate; aryl tosylate unactivated cross coupling Grignard palladium catalyst; biaryl unsym preparation.

Aryl tosylates are attractive substrates for Pd-catalyzed cross-coupling reactions, but they are much less reactive than the more commonly used aryl triflates. The authors report the oxidative addition of aryl tosylates to Pd(PPF-t-Bu)[P(o-tolyl)3] [PPF-t-Bu = 1-diphenylphosphino-2-(di-tert-butylphosphinoethyl)ferrocene] and to Pd(CyPF-t-Bu)[P(o-tolyl)3] [CyPF-t-Bu = 1-dicyclohexylphosphino-2-(di-tert-butylphosphinoethyl)ferrocene] at room temperature to produce the corresponding Pd(II) aryl tosylate complexes (shown as I; R = Ph, X = OTs 3; R = cyclohexyl, X = OTs 4). In the presence of added bromide ions, arylpalladium(II) bromide complexes I (R = Ph, X = Br 5 ; R = cyclohexyl, X = Br 6) were formed. The structures of 5 and 6 were determined by x-ray crystallog. The rate of oxidative addition was accelerated by addition of either coordinating or weakly coordinating anions, and the reactions were faster in more polar solvents. The mild conditions for oxidative addition allowed the development of Pd-catalyzed Kumada couplings and amination reactions of unactivated aryl tosylates at room temperature The catalysts for these mild couplings of aryl tosylates were generated from Pd precursors and the sterically hindered Josiphos-type ligands that induced oxidative addition of aryl tosylates to Pd(0) at room temperature Thus, coupling reaction of XC6H4OTs (X = 2- and 4-MeO, 4-CF3, 4-Me) or of mesityl tosylate or of 1-naphthyl tosylate with aryl Grignard reagents ArMgBr (Ar = 4-tolyl, 4-FC6H4, 4-MeOC6H4) in PhMe in presence of 0.1-1.0 mol % Pd(dba)2 and PPF-t-Bu at either 25° or 80° gave the corresponding biaryls in 40-86% yields.

Journal of the American Chemical Society published new progress about Amination catalysts. 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Application of C32H40FeP2.

Referemce:
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

Larksarp, Chitchamai; Sellier, Odile; Alper, Howard published the artcile< Palladium-Catalyzed Cyclization Reactions of 2-Vinylthiiranes with Heterocumulenes. Regioselective and Enantioselective Formation of Thiazolidine, Oxathiolane, and Dithiolane Derivatives>, COA of Formula: C32H40FeP2, the main research area is thiazolidineimine enantioselective regioselective preparation; thiazolidine oxathiolane dithiolane regioselective preparation; palladium catalyst ring expansion reaction vinylthiirane carbodiimide isocyanate; isothiocyanate keteneimine ketene ring expansion reaction vinylthiirane palladium catalyst; diphosphine ligand enantioselective ring expansion reaction vinylthiirane carbodiimide; heterocumulene ring expansion reaction vinylthiirane palladium catalyst.

Sulfur-containing five-membered-ring heterocycles such as I (R = H, Me; R1 = 4-ClC6H4, 4-BrC6H4, 2-ClC6H4, 4-O2NC6H4, 4-MeC6H4, Ph; X = R1N, O; Y = R1N, S) are prepared by palladium-catalyzed ring expansion reactions of 2-vinylthiirane and 2-methyl-2-vinylthiirane with carbodiimides, isocyanates, isothiocyanates, and ketenimines in the presence of bidentate phosphine ligands such as BINAP or 1,3-bis(diphenylphosphino)propane (dppp). E.g., 2.5 mol% of the chloroform adduct of tris(dibenzylideneacetone)dipalladium and 5 mol% of dppp were stirred in THF under nitrogen pressure for 30 min.; 2 equivalent of 2-vinylthiirane and 1 equivalent of di(4-chlorophenyl)carbodimide were added and the mixture stirred for 24h at 50° to give thiazolidineimine I (R = H; R1 = 4-ClC6H4; X = Y = R1N) in 97% yield. Using nonracemic ligands such as (S)-tol-BINAP and (R)-BINAP in the palladium-catalyzed ring expansion reaction gave the enantiomers of I (R = H; R1 = 4-ClC6H4; X = Y = R1N) in 63 and 68% ee, resp.

Journal of Organic Chemistry published new progress about Carbodiimides Role: RCT (Reactant), RACT (Reactant or Reagent). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, COA of Formula: C32H40FeP2.

Referemce:
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

Roy, Amy H.; Hartwig, John F. published the artcile< Oxidative Addition of Aryl Tosylates to Palladium(0) and Coupling of Unactivated Aryl Tosylates at Room Temperature>, Related Products of 277306-29-3, the main research area is palladium oxidative addition phenyl tosylate mechanism kinetics; crystal structure palladium phenyl bromo ferrocene diphosphine chelate preparation; mol structure palladium phenyl bromo ferrocene diphosphine chelate; aryl tosylate unactivated cross coupling Grignard palladium catalyst; biaryl unsym preparation.

Aryl tosylates are attractive substrates for Pd-catalyzed cross-coupling reactions, but they are much less reactive than the more commonly used aryl triflates. The authors report the oxidative addition of aryl tosylates to Pd(PPF-t-Bu)[P(o-tolyl)3] [PPF-t-Bu = 1-diphenylphosphino-2-(di-tert-butylphosphinoethyl)ferrocene] and to Pd(CyPF-t-Bu)[P(o-tolyl)3] [CyPF-t-Bu = 1-dicyclohexylphosphino-2-(di-tert-butylphosphinoethyl)ferrocene] at room temperature to produce the corresponding Pd(II) aryl tosylate complexes (shown as I; R = Ph, X = OTs 3; R = cyclohexyl, X = OTs 4). In the presence of added bromide ions, arylpalladium(II) bromide complexes I (R = Ph, X = Br 5 ; R = cyclohexyl, X = Br 6) were formed. The structures of 5 and 6 were determined by x-ray crystallog. The rate of oxidative addition was accelerated by addition of either coordinating or weakly coordinating anions, and the reactions were faster in more polar solvents. The mild conditions for oxidative addition allowed the development of Pd-catalyzed Kumada couplings and amination reactions of unactivated aryl tosylates at room temperature The catalysts for these mild couplings of aryl tosylates were generated from Pd precursors and the sterically hindered Josiphos-type ligands that induced oxidative addition of aryl tosylates to Pd(0) at room temperature Thus, coupling reaction of XC6H4OTs (X = 2- and 4-MeO, 4-CF3, 4-Me) or of mesityl tosylate or of 1-naphthyl tosylate with aryl Grignard reagents ArMgBr (Ar = 4-tolyl, 4-FC6H4, 4-MeOC6H4) in PhMe in presence of 0.1-1.0 mol % Pd(dba)2 and PPF-t-Bu at either 25° or 80° gave the corresponding biaryls in 40-86% yields.

Journal of the American Chemical Society published new progress about Amination catalysts. 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Related Products of 277306-29-3.

Referemce:
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

Yen, Andy; Pham, Anh Hoang; Larin, Egor M.; Lautens, Mark published the artcile< Rhodium-Catalyzed Enantioselective Synthesis of Oxazinones via an Asymmetric Ring Opening-Lactonization Cascade of Oxabicyclic Alkenes>, Name: (2S)-1-[(1S)-1-[Bis(1,1-dimethylethyl)phosphino]ethyl]-2-(diphenylphosphino)ferrocene, the main research area is oxabicyclic alkene amino acid ester rhodium ring opening lactonization; oxazinone stereoselective preparation.

The rhodium-catalyzed asym. ring opening reaction of oxabicyclic alkenes is shown to be an efficient method for synthesizing chiral heterocycles. We demonstrate that the pairwise combination of chiral catalyst with chiral amino-acid-derived pronucleophiles results in a stereodivergent synthesis of diastereomeric hydroxyesters. A favorable conformational preference induces the subsequent lactonization of one diastereomer leading to the highly enantioselective synthesis of oxazinones.

Organic Letters published new progress about Alkenes Role: RCT (Reactant), RACT (Reactant or Reagent) (Oxabicyclic). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Name: (2S)-1-[(1S)-1-[Bis(1,1-dimethylethyl)phosphino]ethyl]-2-(diphenylphosphino)ferrocene.

Referemce:
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

Lipshutz, Bruce H.; Lee, Ching-Tien; Taft, Benjamin R. published the artcile< A conjugate reduction pathway to chiral silanes using CuH>, Application In Synthesis of 277306-29-3, the main research area is ester carboxylic silylated chiral preparation asym reduction hydrosilylation enoate; copper hydride ferrocenylphosphine catalyst asym reduction hydrosilylation enoate; silane carboxyalkyl chiral preparation asym reduction silyl enoate.

Asym. reduction of β-silyl α,β-unsaturated esters was achieved by CuH/(R,S)-PPF-P(tBu)2 reagent, affording chiral β-silylated arylalkanoate esters. β-Silyl enoates (Z)- and (E)-PhMe2SiCR:CHCO2R1 [(Z)-2, (E)-2, resp.] were prepared by Peterson or Horner-Wadsworth-Emmons olefination, resp., of the corresponding acylsilanes PhMe2SiCOR. The compounds 2 were reduced by CuH-catalyzed conjugate hydrosilylation by polymethylhydrosiloxane in the presence of chiral ferrocenylphosphine, (R,S)-1-[1-(di-tert-butylphosphino)ethyl]-2-diphenylphosphinoferrocene (1). Exptl. details concerning asym. 1,4-reduction of β-silylated-β,β-disubstituted enoates catalyzed by CuH are described.

Synthesis published new progress about Esters, α,β-unsaturated Role: RCT (Reactant), SPN (Synthetic Preparation), RACT (Reactant or Reagent), PREP (Preparation). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Application In Synthesis of 277306-29-3.

Referemce:
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

Feng, Yuting; Viereck, Peter; Li, Shi-Guang; Tsantrizos, Youla S. published the artcile< Rh(I)-catalyzed asymmetric transfer hydrogenation of α-enamidophosphonates to α-aminophosphonates>, SDS of cas: 277306-29-3, the main research area is rhodium catalyst stereoselective transfer hydrogenation enamidophosphonate mechanism; amino phosphonate preparation stereoselective library.

An asym. Rh-catalyzed transfer hydrogenation was developed for the conversion of α-enamidophosphonates to α-aminophosphonates (α-APs) using isopropanol as the hydride donor. This methodol. is amenable to a broad substrate scope. A library of structurally diverse α-APs was synthesized in moderate to good yield and enantiomeric excess, having a methylene moiety at Cβ and aryl, heteroaryl or alkyl side chains.

Tetrahedronpublished new progress about Enantioselective synthesis. 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, SDS of cas: 277306-29-3.

Referemce:
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