Chiral phosphine ligands

Homogeneous Chiral Nickel-Catalyzed Asymmetric Hydrogenation of Substituted Aromatic α-Aminoketone Hydrochlorides through Dynamic Kinetic Resolution was written by Hibino, Takuya;Makino, Kazuishi;Sugiyama, Takaya;Hamada, Yasumasa. And the article was included in ChemCatChem in 2009.Application of 360048-63-1 This article mentions the following:

Asym. hydrogenation of aromatic amino ketones using homogeneous chiral nickel catalyst proceeds with high diastereoselectivity and excellent enantioselectivity via dynamic kinetic resolution In AcOH the hydrogenation proceeds diastereoselectively with retention of the configuration at the stereogenic center. In the experiment, the researchers used many compounds, for example, (1R)-1-[Bis(4-methoxy-3,5-dimethylphenyl)phosphino]-2-[(1R)-1-(dicyclohexylphosphino)ethyl]ferrocene (cas: 360048-63-1Application of 360048-63-1).

(1R)-1-[Bis(4-methoxy-3,5-dimethylphenyl)phosphino]-2-[(1R)-1-(dicyclohexylphosphino)ethyl]ferrocene (cas: 360048-63-1) belongs to chiral phosphine ligands. Although many reactions require more nucleophilic trialkylphosphines as catalysts, only a few chiral trialkylphosphines are available. Trivalent phosphorus compounds called phosphines have a tetrahedral electron-group geometry which makes them structurally analogous to amines.Application of 360048-63-1

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Ir(I)-catalyzed enantioselective hydrogenolysis of 3-aryl-3-hydroxyisoindolin-1-ones was written by Ge, Chen;Liang, Ren-Xiao;Liu, Ren-Rong;Xiang, Bin;Jia, Yi-Xia. And the article was included in Tetrahedron Letters in 2017.Reference of 133545-16-1 This article mentions the following:

An enantioselective hydrogenolysis of 3-aryl-3-hydroxyisoindolin-1-ones under H₂ was developed by using Ir(I)/(R)-MeO-Biphep complex as a catalyst. Cyclic diaryl methylamides were obtained in moderate to excellent yields and up to 92% ee. In the experiment, the researchers used many compounds, for example, (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) (cas: 133545-16-1Reference of 133545-16-1).

(R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) (cas: 133545-16-1) belongs to chiral phosphine ligands. Generally, the efficiency of nucleophilic phosphine catalysis often depends on the nature of the tertiary phosphine. Asymmetric catalytic performance is determined not only by the metal center but also by the chiral ligand selected.Reference of 133545-16-1

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Catalytic Enantioselective Hydrovinylation of Trialkylsilyloxy and Acetoxy-1,3-Dienes: Cationic Co(I) Complexes for the Synthesis of Chiral Enolate Surrogates and Their Applications for Synthesis of Ketones and Cross-Coupling Reagents in High Enantiomeric Purity was written by Biswas, Souvagya;Dewese, Kendra R.;Raya, Balaram;RajanBabu, T. V.. And the article was included in ACS Catalysis in 2022.Name: (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) This article mentions the following:

(E)-2-Trialkylsilyloxy-1,3-dienes and the corresponding 2-acetoxy derivatives participate in Co-catalyzed heterodimerization reactions with ethylene, giving mostly 4,1-hydrovinylation products with addition of the vinyl group to C₄ and H at C₁ of the diene. The reaction, which gives highly functionalized, protected enolates, is best carried out at room temperature with the diene dissolved in CH₂Cl₂ and ethylene delivered from a balloon in the presence of a catalyst generated in situ by the reaction of (P~P)CoCl₂ with methylaluminoxane (MAO). Com. available chiral ligands, 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis-(diphenylphosphino)butane (DIOP) and 2,4-bis-diphenylphosphinopentane (BDPP) in combination with the earth-abundant metal Co, gave excellent regio- and enantioselectivities (up to 99% ee) for the chiral enolate surrogates from both silyloxy and acetoxydienes. Hydrolyzes of the silyl enol ethers lead to β-vinyl ketones, thus providing a practical two-step approach to these valuable synthons starting from α,β-unsaturated ketones and ethylene. The hydrovinylated silyl enol ethers undergo typical nucleophilic reactions such as alkylation, aldol, and Michael and Mannich reactions with varying degrees of diastereoselectivity (2:1-13:1). The silyl enol ethers are convenient sources of Li enolates, which are readily converted into other vinyl derivatives such as vinyl acetates and vinyl triflates. The vinyl triflates are excellent partners for cross-coupling chem., giving potentially useful, polyolefinic chiral synthons for further applications. Chemoselective reduction and hydrosilylation of the vinyl group in the chiral β-vinyl silyl enol ether further illustrate other potential reactivities of these versatile synthons. Since isolated cationic [(P~P)Co(I)]⁺ [BARF]^– appears to be an excellent catalyst for the heterodimerization of silyl enol ethers and ethylene giving products very similar in yield and selectivities to what is observed in the MAO-mediated reactions, probably a previously invoked Co(I)/Co(III) cycle, common to other similar heterodimerization reactions, might be involved in these reactions as well. In the experiment, the researchers used many compounds, for example, (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) (cas: 77876-39-2Name: (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine)).

(2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) (cas: 77876-39-2) belongs to chiral phosphine ligands. Many phosphine-catalyzed reactions have been developed for the syntheses of various biologically important acyclic and cyclic molecules. Asymmetric variants of these reactions have evolved relatively slowly. Asymmetric catalytic performance is determined not only by the metal center but also by the chiral ligand selected.Name: (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Chiral discrimination at the η³-allyl units of rhodium(I) η³-cyclooctenyl complexes containing chiral bidentate phosphines was written by Lange, Susanne;Wittmann, Klaus;Gabor, Barbara;Mynott, Richard;Leitner, Walter. And the article was included in Tetrahedron: Asymmetry in 1998.Recommanded Product: (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) This article mentions the following:

A three step synthesis of Rh(I) η³-cyclooctenyl complexes [(P₂^*)Rh(η³-C₈H₁₃)] (P₂^* = chiral bidentate phosphine, e.g. (S,S)-4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane) starting from com. available [{(cod)Rh(μ-Cl)}₂] is described. Examination of these complexes by multinuclear NMR-spectroscopy reveals a distinct stereochem. differentiation of the terminal positions of the η³-allyl unit. Preliminary results on the reactivity of these compounds towards various electrophiles E-X (e.g. MeOTf) are reported; hydrogen transfer is preferred over formation of C-E bonds. In the experiment, the researchers used many compounds, for example, (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) (cas: 77876-39-2Recommanded Product: (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine)).

(2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) (cas: 77876-39-2) belongs to chiral phosphine ligands. The synthesis of novel trialkylphosphines can be quite difficult, thereby limiting the scope of their chiral variants. Over the last decade, however, and especially since 2005, considerable progress has been made in asymmetric phosphine catalysis.Recommanded Product: (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Enantioselective α-Allylation of Anilines Enabled by a Combined Palladium and Photoredox Catalytic System was written by Zhang, Hong-Hao;Zhao, Jia-Jia;Yu, Shouyun. And the article was included in ACS Catalysis in 2020.HPLC of Formula: 352655-61-9 This article mentions the following:

An enantioselective and branch-regioselective α-allylation of N-Me anilines with allylic acetates under dual palladium/photoredox catalysis was described. Readily available N-Me anilines were used as formal ”hard” alkyl nucleophiles without preactivation. Acetic acid was the only side product, which led to a high atom economy of this reaction. This protocol showed good functional group tolerance and broad scope. A range of chiral homoallylic amines I [R = Me, i-Pr, Ph, etc.; Ar¹ = Ph, 4-MeOC₆H₄, 4-NHAcC₆H₄, etc.; Ar² = Ph, 3-MeC₆H₄, 4-ClC₆H₄, etc.] were prepared in moderate to good yields (up to 76%) and excellent regioselectivities (B:L > 95:5 in all cases) and enantioselectivities (up to 96% ee) under mild reaction conditions. In the experiment, the researchers used many compounds, for example, (R)-(-)-2,2′-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-6,6′-dimethoxy-1,1′-biphenyl (cas: 352655-61-9HPLC of Formula: 352655-61-9).

(R)-(-)-2,2′-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-6,6′-dimethoxy-1,1′-biphenyl (cas: 352655-61-9) belongs to chiral phosphine ligands. Phosphine-catalyzed asymmetric reactions are now powerful and versatile tools for the construction of C–C, C–N, C–O, and C–S bonds and for the syntheses of functionalized carbocycles and heterocycles. Chiral phosphine catalysts: Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates.HPLC of Formula: 352655-61-9

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Ligand-Substrate Dispersion Facilitates the Copper-Catalyzed Hydroamination of Unactivated Olefins was written by Lu, Gang;Liu, Richard Y.;Yang, Yang;Fang, Cheng;Lambrecht, Daniel S.;Buchwald, Stephen L.;Liu, Peng. And the article was included in Journal of the American Chemical Society in 2017.Category: chiral-phosphine-ligands This article mentions the following:

The current understanding of ligand effects in transition metal catalysis is mostly based on the anal. of catalyst-substrate through-bond and through-space interactions, with the latter commonly considered to be repulsive in nature. The dispersion interaction between the ligand and the substrate, a ubiquitous type of attractive noncovalent interaction, is seldom accounted for in the context of transition-metal-catalyzed transformations. Herein we report a computational model to quant. analyze the effects of different types of catalyst-substrate interactions on reactivity. Using this model, we show that in the copper(I) hydride (CuH)-catalyzed hydroamination of unactivated olefins, the substantially enhanced reactivity of copper catalysts based on bulky bidentate phosphine ligands originates from the attractive ligand-substrate dispersion interaction. These computational findings are validated by kinetic studies across a range of hydroamination reactions using structurally diverse phosphine ligands, revealing the critical role of bulky P-aryl groups in facilitating this process. In the experiment, the researchers used many compounds, for example, (R)-(-)-2,2′-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-6,6′-dimethoxy-1,1′-biphenyl (cas: 352655-61-9Category: chiral-phosphine-ligands).

(R)-(-)-2,2′-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-6,6′-dimethoxy-1,1′-biphenyl (cas: 352655-61-9) belongs to chiral phosphine ligands. At present, the synthesis of new chiral phosphines designed specifically for nucleophilic organocatalysis remains a significant challenge. Effective chiral catalysts for nucleophilic phosphine catalysis are scarce, seriously limiting the development of asymmetric variants. Category: chiral-phosphine-ligands

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Total synthesis of the antimalarial naphthylisoquinoline alkaloid 5-epi-4′-O-demethylancistrobertsonine C by asymmetric Suzuki cross-coupling was written by Bringmann, Gerhard;Ruedenauer, Stefan;Bruhn, Torsten;Benson, Lauren;Brun, Reto. And the article was included in Tetrahedron in 2008.COA of Formula: C26H28FeNP This article mentions the following:

The first total synthesis of the antimalarial naphthylisoquinoline alkaloid 5-epi-4′-O-demethylancistrobertsonine C (I) and its-as yet unnatural-atropo-diastereomer is described. The key step of the synthesis is the construction of the rotationally hindered and thus stereogenic biaryl axis, which was built up by a Suzuki reaction. The use of chiral ligands in the palladium-catalyzed cross-coupling permitted to increase the low internal asym. induction up to a diastereomeric ratio of 74:26. The assignment of the axial configurations of the atropo-diastereomers was achieved by 2D NMR experiments and corroborated by quantum chem. CD calculations In the experiment, the researchers used many compounds, for example, (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2COA of Formula: C26H28FeNP).

(R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2) belongs to chiral phosphine ligands. Many phosphine-catalyzed reactions have been developed for the syntheses of various biologically important acyclic and cyclic molecules. Asymmetric variants of these reactions have evolved relatively slowly. Indeed, very little research on chiral tertiary phosphine-catalyzed asymmetric reactions occurred prior to the year 2000.COA of Formula: C26H28FeNP

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Compromise between conjugation length and charge-transfer in nonlinear optical η⁵-monocyclopentadienyliron(II) complexes with substituted oligo-thiophene nitrile ligands: Synthesis, electrochemical studies and first hyperpolarizabilities was written by Garcia, M. Helena;Mendes, Paulo J.;Robalo, M. Paula;Dias, A. Romao;Campo, Jochen;Wenseleers, Wim;Goovaerts, Etienne. And the article was included in Journal of Organometallic Chemistry in 2007.Recommanded Product: 37002-48-5 This article mentions the following:

A series of half-sandwich η⁵-cyclopentadienyliron(II) diphosphine complexes with substituted oligo-thiophene carbonitrile ligands, [FeCp(P-P)(NC{SC₄H₂}_nNO₂)][PF₆] (1a–3a, P-P = dppe; 1b–3b, P-P = (+)-diop; n = 1-3) was prepared by complexation of the nitrile ligands to the corresponding iodides, [FeCp(P-P)I]. The electrochem. behavior of the new compounds was explored by cyclic voltammetry. The compounds 1–3 exhibit pos. solvatochromism, i.e., a bathochromic shift in more polar solvents. Quadratic hyperpolarizabilities (β) of the complexes with dppe co-ligands have been determined by hyper-Rayleigh scattering (HRS) measurements at two fundamental wavelengths of 1.064 and 1.550 μm, to uncover the two-photon resonance effect and to estimate static β values. The obtained overall results are found to be better than for the related η⁵-monocyclopentadienyliron(II) complexes with p-benzonitrile derivatives Although an increase of the resonant β at 1.064 μm with increasing number of thiophene units in the conjugated ligand was found (up to 910 × 10^-30 esu), the static values β₀ remain practically unchanged, as shown by the 1.550 μm measurements. Combined with the electrochem. and spectroscopic data (IR, NMR, UV-vis), this remarkable evolution of β shows that the increase of conjugation length is balanced by a decrease in charge-transfer efficiency. In the experiment, the researchers used many compounds, for example, (((4S,5S)-2,2-Dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene))bis(diphenylphosphine) (cas: 37002-48-5Recommanded Product: 37002-48-5).

(((4S,5S)-2,2-Dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene))bis(diphenylphosphine) (cas: 37002-48-5) belongs to chiral phosphine ligands. Phosphine-catalyzed asymmetric reactions are now powerful and versatile tools for the construction of C–C, C–N, C–O, and C–S bonds and for the syntheses of functionalized carbocycles and heterocycles. Chiral ligands coordinate to metal centers to create an asymmetric environment around the reaction centers, which eventually affects enantioselectivity and reaction rate.Recommanded Product: 37002-48-5

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Palladium-catalysed intramolecular asymmetric cyclohydroaryloxycarbonylation of 2-allylphenol derivatives. Synthesis of chiral lactones via cyclocarbonylation was written by Abu Seni, Anas;Kollar, Laszlo;Pongracz, Peter. And the article was included in Molecular Catalysis in 2020.Related Products of 37002-48-5 This article mentions the following:

Homogeneous catalytic hydroaryloxycarbonylation of 2-allylphenol derivatives I (R¹ = H, CH₃, OCH₃, CHO; R² = H, COCH₃) was performed using palladium complexes toward the corresponding lactones II, III, IV. Reactions were conducted under carbon monoxide atm. in the absence of hydrogen gas. Palladium catalyst was generated in situ, using various phosphine ligands e.g., (4S,5S)-4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane and precursors as Pd(OAc)₂, PdCl₂, PdCl₂(PhCN)₂, etc. in the presence of acid additives as HCl, HCOOH, TsOH, etc. In general, chiral 6- III and achiral 7-membered lactones IV were formed dominantly, only trace amounts of the 5-membered lactone II can be identified. Moderate or good enantioselectivity can be achieved using chiral ligands regarding the 6-membered chromanone derivatives III. The regioselectivity of the reaction is particularly effected by catalyst composition and acid co-catalysts and found to be insensitive for substrate substitution. In the experiment, the researchers used many compounds, for example, (((4S,5S)-2,2-Dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene))bis(diphenylphosphine) (cas: 37002-48-5Related Products of 37002-48-5).

(((4S,5S)-2,2-Dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene))bis(diphenylphosphine) (cas: 37002-48-5) belongs to chiral phosphine ligands. The synthesis of novel trialkylphosphines can be quite difficult, thereby limiting the scope of their chiral variants. Effective chiral catalysts for nucleophilic phosphine catalysis are scarce, seriously limiting the development of asymmetric variants. Related Products of 37002-48-5

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Enantioface-Selective Palladium-Catalyzed Silaboration of Allenes via Double Asymmetric Induction was written by Suginome, Michinori;Ohmura, Toshimichi;Miyake, Yoshihiro;Mitani, Shin’ichirou;Ito, Yoshihiko;Murakami, Masahiro. And the article was included in Journal of the American Chemical Society in 2003.Computed Properties of C33H25OP This article mentions the following:

Enantioenriched β-borylallylsilanes, e.g., (RO)₂BC(:CH₂)CH(SiMe₂Ph)CH₂CH₂Ph [(RO)₂B = 4,5-diorgano-1,3,2-dioxaborolanyl], were synthesized by Pd-catalyzed enantioface-selective addition of the Si-B bond of chiral 2-dimethylsilyl-4,5-diorgano-1,3,2-dioxaborolane (e.g., organo = Me, Ph, CO₂Prⁱ) to terminal allenes, CH₂:C:CHCH₂CH₂Ph, using a Pd catalyst possessing a chiral monodentate phosphine ligand, e.g., CpPd(allyl)/PPh₃. Use of a silylborane bearing a chiral auxiliary on the B atom was beneficial to gain enantioface selectivities ≤96% de. In the experiment, the researchers used many compounds, for example, (S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine (cas: 134484-36-9Computed Properties of C33H25OP).

(S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine (cas: 134484-36-9) belongs to chiral phosphine ligands. During the past two decades, tertiary phosphine catalysts have been applied extensively in a wide range of carbon–carbon and carbon–heteroatom bond-forming transformations. Most of these phosphines are acyclic, usually possess low nucleophilic activity, and generally display poor enantioselectivities for phosphine organocatalysis. Computed Properties of C33H25OP

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis