Chiral phosphine ligands

Renom-Carrasco, Marc’s team published research in Chemistry – A European Journal in 2016 | 277306-29-3

Chemistry – A European Journal published new progress about Bases Role: RGT (Reagent), RACT (Reactant or Reagent). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Category: chiral-phosphine-ligands.

Renom-Carrasco, Marc; Gajewski, Piotr; Pignataro, Luca; de Vries, Johannes G.; Piarulli, Umberto; Gennari, Cesare; Lefort, Laurent published the artcile< Asymmetric Hydrogenation of 3-Substituted Pyridinium Salts>, Category: chiral-phosphine-ligands, the main research area is pyridinium salt asym hydrogenation; asymmetric catalysis; homogeneous catalysis; hydrogenation; pyridines; reaction mechanisms.

The use of an equivalent amount of an organic base leads to high enantiomeric excess in the asym. hydrogenation of N-benzylated 3-substituted pyridinium salts into the corresponding piperidines. Indeed, in the presence of Et3N, a Rh-JosiPhos catalyst reduced a range of pyridinium salts with ee values up to 90%. The role of the base was elucidated with a mechanistic study involving the isolation of the various reaction intermediates and isotopic labeling experiments Addnl., this study provided some evidence for an enantiodetermining step involving a dihydropyridine intermediate.

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

Ashizawa, Tomoko’s team published research in Chemistry Letters in 2009-03-05 | 139139-93-8

Chemistry Letters published new progress about Aromatic esters Role: SPN (Synthetic Preparation), PREP (Preparation) (biaryl). 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Category: chiral-phosphine-ligands.

Ashizawa, Tomoko; Yamada, Tohru published the artcile< Catalytic atropo-enantioselective preparation of axially chiral biaryl compounds>, Category: chiral-phosphine-ligands, the main research area is biaryl lactone methanol chiral silver catalyst triisobutylamine ring opening; ester biaryl hydroxy derivative atropo stereoselective preparation; silver tetrafluoroborate binap derivative dynamic kinetic resolution catalyst.

The atropo-enantioselective ring-opening of biaryl lactones with methanol was catalyzed by an optically active AgBF4-phosphine complex to afford axially chiral biaryl compounds The addition of triisobutylamine provided a rate acceleration and increase in enantioselectivity in the reaction. Various types of axially chiral biaryl compounds were obtained with high enantioselectivity.

Alexy, Eric J’s team published research in Journal of the American Chemical Society in 2018-08-15 | 152140-65-3

Journal of the American Chemical Society published new progress about Allylic alkylation. 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, HPLC of Formula: 152140-65-3.

Alexy, Eric J.; Zhang, Haiming; Stoltz, Brian M. published the artcile< Catalytic Enantioselective Synthesis of Acyclic Quaternary Centers: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Acyclic Enol Carbonates>, HPLC of Formula: 152140-65-3, the main research area is enol carbonate acyclic palladium phosphinooxazoline decarboxylative allylic alkylation catalyst; ketone quaternary stereoselective preparation.

The first enantioselective palladium-catalyzed decarboxylative allylic alkylation of fully substituted acyclic enol carbonates providing linear α-quaternary ketones is reported. Investigation into the reaction revealed that the use of an electron-deficient phosphinooxazoline ligand renders the enolate geometry of the starting material inconsequential, with the same enantiomer of product obtained in the same level of selectivity regardless of the starting ratio of enolates. As a result, a general method toward acyclic all-carbon quaternary stereocenters has been developed.

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.

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.