October 2022 | Page 35 of 44 | Chiral phosphine ligands

Augustine, Robert’s team published research in Chemical Industries (Boca Raton, FL, United States) in 2007 | 325168-88-5

Chemical Industries (Boca Raton, FL, United States) published new progress about Chiral ligands Role: CAT (Catalyst Use), USES (Uses). 325168-88-5 belongs to class chiral-phosphine-ligands, and the molecular formula is C48H50P2, Application of C48H50P2.

Augustine, Robert; Tanielyan, Setrak; Marin, Norman; Alvez, Gabriela published the artcile< Synthesis of chiral 2-amino-1-phenylethanol>, Application of C48H50P2, the main research area is aminophenylethanol stereoselective preparation phenacyl chloride.

Two methods for the synthesis of chiral 2-amino-1-phenylethanol have been developed. The first uses a chiral oxaborolidine catalyzed borane reduction of phenacyl chloride to give the chiral chloro alc. in very good yield with an ee in the 93%-97% range. Reaction with dilute ammonium hydroxide produced the amino alc. in very good yield with a high ee. The second approach involved the conversion of phenacyl chloride to the succinimide which was then hydrogenated using a chiral ruthenium complex in conjunction with a base and an optically active amine (Noyori procedure) to give the optically active succinimido alc. in very good yield with an ee of 98%. Hydrolysis with dilute base produced the optically active amino alc. in very good yield and excellent enantioselectivity.

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

Pandey, Krishna K’s team published research in Inorganic Chemistry in 2009-04-06 | 606-68-8

Inorganic Chemistry published new progress about Bond. 606-68-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C21H27N7Na2O14P2, Name: ((2R,3S,4R,5R)-5-(6-Aminopurin-9-yl)-3,4-dihydroxy-oxolan-2-yl)methoxy-((((2R,3S,4R,5R)-5-(3-carbamoyl-4H-pyridin-1-yl)-3,4-dihydroxy-oxolan-2-yl)methoxy)hydroxyphosphoryl)oxyphosphinic acid disodium salt.

Pandey, Krishna K.; Lledos, Agusti published the artcile< Linear ME-Me Versus Bent M-E-Me: Bonding Analysis in Heavier Metal-ylidyne Complexes [(Cp)(CO)2MEMe] and Metallo-ylidenes [(Cp)(CO)3M-EMe] (M = Cr, Mo, W; E = Si, Ge, Sn, Pb)>, Name: ((2R,3S,4R,5R)-5-(6-Aminopurin-9-yl)-3,4-dihydroxy-oxolan-2-yl)methoxy-((((2R,3S,4R,5R)-5-(3-carbamoyl-4H-pyridin-1-yl)-3,4-dihydroxy-oxolan-2-yl)methoxy)hydroxyphosphoryl)oxyphosphinic acid disodium salt, the main research area is bonding analysis transition metal ylidyne complex.

The electronic and mol. structures of the complexes [(η5-C5H5)(CO)2MEMe] and [(η5-C5H5)(CO)3M-EMe] (M = Cr, Mo, W; E = Si, Sn, Pb) are calculated at the d.-functional theory (DFT) level using the exchange correlation functionals B3LYP and BP86. The theor. predicted bond lengths and angles of the model compounds are in excellent agreement with exptl. values. The calculations reveal the presence of a strong ME triple (σ + 2π) bond in [(η5-C5H5)(CO)2MEMe]. The M-E bond lengths in [(η5-C5H5)(CO)3M-EMe] are longer than those expected for a single bond. The nature of the MEMe and M-EMe interactions was analyzed with charge and energy decomposition methods. In the MEMe bond, the M-E σ-bonding orbitals are always polarized toward the silicon, tin, and lead atoms, and the polarization increases from chromium to tungsten. In contrast, in the M-EMe bond, the M-E σ-bonding orbitals are significantly polarized toward the metal atom. The hybridization at the metal atoms in the ME bonds has d character in the range 60.6-68.8%, while in the M-E bonds has large d character which is always >86% of the total AO contribution. In the complexes [(η5-C5H5)(CO)2MEMe], the contributions of the electrostatic interactions, ΔEelstat, and the covalent bonding, ΔEorb, have nearly the same values for silylidyne and germylidyne complexes, while for the stannylidyne and plumbylidyne complexes, the electrostatic interactions, ΔEelstat, are greater than the orbital interaction, ΔEorb. The covalent bonding has a high degree of π-character. The total interaction energy ΔEint in the compound [(η5-C5H5)(CO)3M-EMe] is less attractive than those in the complexes [(η5-C5H5)(CO)2MEMe]. The M-ER bonds have a slightly lower degree of covalent bonding (34.9-44.9%) than the MEMe bonds (42.1-50.2%). The drastic difference between the two classes of compounds are found for the degree of a” (π) bonding. The contribution of ΔEπ to the covalent term ΔEorb is much higher in the MEMe bonding (41.6-42.6%) than in the M-EMe bonding (17.1-20.4%). While the π bonding contribution in [(η5-C5H5)(CO)3M-EMe] are weaker than those in [(η5-C5H5)(CO)2MEMe], the σ-bonding contribution in the former compounds are stronger than those in the latter.

Zhang, Xiaoyong’s team published research in Tetrahedron Letters in 1991-12-02 | 139139-86-9

Tetrahedron Letters published new progress about 139139-86-9. 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Application of C44H40P2.

Zhang, Xiaoyong; Mashima, Kazushi; Koyano, Kinko; Sayo, Noboru; Kumobayashi, Hidenori; Akutagawa, Susumu; Takaya, Hidemasa published the artcile< Synthesis of partially hydrogenated BINAP variants>, Application of C44H40P2, the main research area is BINAP hydrogenated; crystal structure cyclohexylphosphinylbinaphthyl; mol structure cyclohexylphosphinylbinaphthyl; binaphthyl hydro atropisomeric phosphine ligand.

Three pairs of new axially dissym. diphosphine ligands, (R)-(-)- and (S)-(+)-2,2′-bis(dicyclohexylphosphino)-1,1′-binaphthyl, (R)-(+)- and (S)-(-)-2,2′-bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl and (R)-(-)- and (S)-(+)-2,2′-bis(dicyclohexylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, have been synthesized and their absolute configurations have been determined on the basis of an x-ray anal. and CD spectra.

Tetrahedron Letters published new progress about 139139-86-9. 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Application of C44H40P2.

Webster, Robert’s team published research in Journal of the American Chemical Society in 2009-01-21 | 277306-29-3

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

Webster, Robert; Boeing, Christian; Lautens, Mark published the artcile< Reagent-controlled regiodivergent resolution of unsymmetrical oxabicyclic alkenes using a cationic rhodium catalyst>, Related Products of 277306-29-3, the main research area is dihydronaphthalenol derivative asym preparation; oxabenzonorbornene derivative preparation nucleophile ring opening reaction rhodium; rhodium asym ring opening reaction catalyst.

A Rh(I) catalyzed regiodivergent addition of heteroatom nucleophiles to racemic oxabicyclic alkenes produces good yields of regioisomeric products each in high ee. Powerful reagent control is demonstrated, as the inherent reactivity of the substrate is completely dominated by the chiral catalyst complex, which is shown to require the use of cationic Rh(I). The process affords rapid access to multiple 1,2-dihydronaphthalene products in high enantioselectivity from simple starting materials.

Yasui, Takeshi’s team published research in Advanced Synthesis & Catalysis in 2021-09-07 | 139139-93-8

Advanced Synthesis & Catalysis published new progress about [2+2+2] Cycloaddition reaction (stereoselective). 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Name: (S)-(-)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl.

Yasui, Takeshi; Nakazato, Yuya; Kurisaki, Koutarou; Yamamoto, Yoshihiko published the artcile< Enantioselective Construction of 5-6-5 Tricyclic Lactone Framework Bearing a Quaternary Bridgehead Carbon via Rh-Catalyzed Asymmetric [2+2+2] Cycloaddition of Enediynes>, Name: (S)-(-)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is tricyclic cyclohexadiene lactone preparation enantioselective; enediyne cycloaddition rhodium catalyst.

Herein, a Rh-catalyzed asym. [2+2+2] cycloaddition of ene-yne-yne enediynes to generate enantio-enriched tricyclic cyclohexadienes bearing a quaternary bridgehead carbon is reported. The Rh-Phanephos complex is an appropriate catalyst for the cycloaddition of enediynes bearing an unsubstituted propiolate terminus, whereas Rh-biaryl bisphosphine catalysts, which have been widely used for asym. cycloadditions of alkynes and alkenes, are not applicable for the reaction of such enediynes. Several control experiments suggest that the reaction using the Rh-Phanephos complex exclusively proceeds via a rhodacyclopentadiene intermediate, unlike when using a Rh-biaryl bisphosphine complex that can form a rhodacyclopentadiene intermediate as well as a rhodacyclopentene intermediate in a substrate-dependent manner.

Duan, Ying’s team published research in Chemistry – A European Journal in 2011 | 139139-86-9

Chemistry – A European Journal published new progress about Aldehydes Role: RCT (Reactant), RACT (Reactant or Reagent). 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Name: (R)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl.

Duan, Ying; Chen, Mu-Wang; Ye, Zhi-Shi; Wang, Duo-Sheng; Chen, Qing-An; Zhou, Yong-Gui published the artcile< An enantioselective approach to 2,3-disubstituted indolines through consecutive Bronsted Acid/Pd-complex-promoted tandem reactions>, Name: (R)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is indoline chiral preparation tandem condensation asym hydrogenation indole aldehyde; hydrogenation catalyst asym palladium BINAP SynPhos complex indoline preparation; indole alkylation reductive tandem preparation chiral indoline.

Chiral substituted indolines, R1-2-R2-3-CH2R3-2,3-dihydro-1H-indoles (3, R1 = H, 5-F, 7-Me; R2 = Me, Bu, CH2CH2Ph; R3 = Ph, 4-MeOC6H4, 4-FC6H4, cyclohexyl, iPr) were prepared by tandem aldol addition-asym. hydrogenation reaction of R1-2-R2-1H-indoles with aldehydes R3CHO, catalyzed by TsOH and Pd-BINAP complexes. The reaction mechanism comprises Bronsted acid-catalyzed condensation and formation of 3-alkylideneiminium intermediate, which is then hydrogenated by in situ formed palladium diphosphine complexes, the (R)-H8-BINAP and (R)-SynPhos [2,2′,3,3′-tetrahydro[5,5′-bi-1,4-benzodioxin]-6,6′-bis(diphenylphosphine)] being the most effective ligands.

Yasuda, Shigeo’s team published research in Chemistry – A European Journal in 2016 | 139139-93-8

Chemistry – A European Journal published new progress about [2+2+2] Cycloaddition reaction. 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, SDS of cas: 139139-93-8.

Yasuda, Shigeo; Kawaguchi, Yasuaki; Okamoto, Yuta; Mukai, Chisato published the artcile< Chemo- and Regioselective Rhodium(I)-Catalyzed [2+2+2] Cycloaddition of Allenynes with Alkynes>, SDS of cas: 139139-93-8, the main research area is allenyne alkyne rhodium cycloaddition catalyst; benzene fused bicyclic preparation; alkynes; allenes; cycloaddition; regioselectivity; rhodium.

A highly chemo- and regioselective partially intramol. rhodium(I)-catalyzed [2+2+2] cycloaddition of allenynes with alkynes is described. A range of diverse polysubstituted benzene derivatives could be synthesized in good to excellent yields, in which the allenynes served as synthetic equivalent to the diynes. A high regioselectivity could be observed when allenynes were treated with unsym. alkynes.

Tian, Shengjun’s team published research in Chemistry of Materials in 2005-11-15 | 606-68-8

Chemistry of Materials published new progress about Colloidal crystals. 606-68-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C21H27N7Na2O14P2, COA of Formula: C21H27N7Na2O14P2.

Tian, Shengjun; Wang, Jianjun; Jonas, Ulrich; Knoll, Wolfgang published the artcile< Inverse Opals of Polyaniline and Its Copolymers Prepared by Electrochemical Techniques>, COA of Formula: C21H27N7Na2O14P2, the main research area is polyaniline composite inverse opal electrochem preparation electrocatalyst.

Ordered 3D arrays of polyaniline (PANI) inverse opals were fabricated via electrochem. methods by using colloidal crystals of polystyrene beads as sacrificial templates. Compared with films obtained by chem. synthesis, the inverse opaline samples obtained by electrochem. had a much higher structural quality. To explore potential biosensing applications, PANI composite inverse opals were fabricated for the first time by modifying the structure with different dopants, such as poly(acrylic acid) (PAA) and poly(styrene sulfonate) (PSS). It was found that these dopants had a major effect on the structure of the obtained opaline films. With selection of suitable dopants, PANI composite inverse opals could be fabricated with very high quality. The obtained films remained electroactive in buffer solutions of neutral pH. Owing to their huge surface area, they should be ideal candidates for biosensing applications, e.g., as electrocatalysts or bioreactors. Our first effort to use such macroporous structures as electrocatalysts for the oxidation of reduced β-NAD (NADH) showed that the electrocatalytic efficiency of the inverse opaline film was much higher compared with that of an unpatterned film.

Lautens, Mark’s team published research in Journal of the American Chemical Society in 2000-06-14 | 277306-29-3

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.

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.

Oonishi, Yoshihiro’s team published research in Angewandte Chemie, International Edition in 2019 | 139139-93-8

Angewandte Chemie, International Edition published new progress about Alcohols, unsaturated Role: RCT (Reactant), SPN (Synthetic Preparation), RACT (Reactant or Reagent), PREP (Preparation). 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Reference of 139139-93-8.

Oonishi, Yoshihiro; Masusaki, Shuichi; Sakamoto, Shunki; Sato, Yoshihiro published the artcile< Rhodium(I)-Catalyzed Enantioselective Cyclization of Enynes by Intramolecular Cleavage of the Rh-C Bond by a Tethered Hydroxy Group>, Reference of 139139-93-8, the main research area is acyl heterocyclic compound enantioselective preparation; enynol preparation enantioselective cyclization rhodium catalyst; cyclization; enantioselectivity; enyne; rhodium; σ-bond metathesis.

Rhodium(I)-catalyzed enantioselective intramol. cyclization of enynes having a hydroxy group in the tether was investigated, and various cyclic compounds possessing a chiral quaternary carbon center were obtained in high yields with high ees. In this cyclization, a Rh-C(sp2) bond in the rhodacyclopentene intermediate, which was formed by enantioselective oxidative cycloaddition of enynes to a chiral rhodium(I) complex, was intramolecularly cleaved by σ-bond metathesis of a tethered O-H bond in the substrate. Furthermore, it was found that the cyclic compounds were obtained with high ees even when the starting materials having a racemic secondary alc. moiety were used in this reaction.