Chiral phosphine ligands

A Mixed-Ligand Approach Enables the Asymmetric Hydrogenation of an α-Isopropylcinnamic Acid en Route to the Renin Inhibitor Aliskiren was written by Boogers, Jeroen A. F.;Felfer, Ulfried;Kotthaus, Martina;Lefort, Laurent;Steinbauer, Gerhard;De Vries, Andre H. M.;De Vries, Johannes G.. And the article was included in Organic Process Research & Development in 2007.Recommanded Product: 864529-90-8 This article mentions the following:

An asym. hydrogenation of (E)-2-isopropyl-3-[3-(3-methoxypropoxy)-4-methoxyphenyl]-2-propenoic acid, which affords a chiral intermediate for the renin inhibitor aliskiren, has been developed using a rhodium catalyst ligated with a chiral monodentate phosphoramidite and a nonchiral phosphine. Whereas catalysts based on two equivalent of monodentate phosphoramidites gave promising results, the rate of hydrogenation and ee of the product could be improved spectacularly by the addition of monodentate nonchiral triarylphosphines to these catalysts. This remarkable mixed-ligand catalyst has been identified using high-throughput experimentation. With the best catalysts turnover numbers >5000 mol mol^-1, turnover frequencies >1000 mol mol^-1 h^-1, and ee’s up to 95% have been achieved. In the experiment, the researchers used many compounds, for example, 1-((11bR)-2,6-Dimethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-yl)piperidine (cas: 864529-90-8Recommanded Product: 864529-90-8).

1-((11bR)-2,6-Dimethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-yl)piperidine (cas: 864529-90-8) belongs to chiral phosphine ligands. Although many reactions require more nucleophilic trialkylphosphines as catalysts, only a few chiral trialkylphosphines are available. Chiral phosphine catalysts: Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates.Recommanded Product: 864529-90-8

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Enantioselective and Regio-divergent Addition of Purines to Terminal Allenes: Synthesis of Abacavir was written by Thieme, Niels;Breit, Bernhard. And the article was included in Angewandte Chemie, International Edition in 2017.Formula: C42H56FeO2P2 This article mentions the following:

The rhodium-catalyzed atom-economic asym. N-selective intermol. addition of purine derivatives to terminal allenes is reported. Branched allylic purines were obtained in high yields, regioselectivity and outstanding enantioselectivity utilizing a Rh/Josiphos catalyst. Conversely, linear selective allylation of purines could be realized in good to excellent regio- and E/Z-selectivity with a Pd/dppf catalyst system. Furthermore, the new methodol. was applied to a straightforward asym. synthesis of carbocyclic nucleoside abacavir. 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: 360048-63-1Formula: C42H56FeO2P2).

(1R)-1-[Bis(4-methoxy-3,5-dimethylphenyl)phosphino]-2-[(1R)-1-(dicyclohexylphosphino)ethyl]ferrocene (cas: 360048-63-1) 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.Formula: C42H56FeO2P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Catalytic enantioselective addition of phenylboronic acid and phenylboroxine to N-tosylimines: Pd^II and Rh^I catalysis was written by Marques, Carolina S.;Burke, Anthony J.. And the article was included in European Journal of Organic Chemistry in 2010.COA of Formula: C52H44N2O2P2 This article mentions the following:

This is the first account of a successful, Pd^II-catalyzed enantioselective addition of phenylboronic acid to electron-deficient N-tosylarylimines by using chiral diphosphane ligands. A number of com. diphosphane ligands were screened. Despite moderate to good yields, ee values of 99% could be achieved with MeDuPhos. Novel Rh^I catalysts were also screened, and ee values as high as 74% could be obtained. In the experiment, the researchers used many compounds, for example, N,N’-((1R,2R)-Cyclohexane-1,2-diyl)bis(2-(diphenylphosphino)-1-naphthamide) (cas: 174810-09-4COA of Formula: C52H44N2O2P2).

N,N’-((1R,2R)-Cyclohexane-1,2-diyl)bis(2-(diphenylphosphino)-1-naphthamide) (cas: 174810-09-4) belongs to chiral phosphine ligands. At present, the synthesis of new chiral phosphines designed specifically for nucleophilic organocatalysis remains a significant challenge. Chiral phosphine catalysts: Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates.COA of Formula: C52H44N2O2P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Synthesis of β-Boryl-α-Aminosilanes by Copper-Catalyzed Aminoboration of Vinylsilanes was written by Kato, Kodai;Hirano, Koji;Miura, Masahiro. And the article was included in Angewandte Chemie, International Edition in 2016.Safety of (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) This article mentions the following:

A Cu-catalyzed regioselective and stereospecific aminoboration of vinylsilanes with bis(pinacolato)diboron (pinB-Bpin) and hydroxylamines was developed. In the presence of a CuCl/MeO-dppbz catalyst, the boryl group and amino group are incorporated at the β position and α position, resp., and the corresponding β-boryl-α-aminosilanes were obtained with good diastereoselectivity. The boryl group is a good latent functional group, and subsequent manipulations provide a variety of β-functionalized α-aminosilanes of great potential in medicinal chem. Addnl., preliminary application to asym. catalysis is also described. In the experiment, the researchers used many compounds, for example, (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) (cas: 77876-39-2Safety of (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine)).

(2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) (cas: 77876-39-2) 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. Effective chiral catalysts for nucleophilic phosphine catalysis are scarce, seriously limiting the development of asymmetric variants. Safety of (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Rapid virtual screening of enantioselective catalysts using CatVS was written by Rosales, Anthony R.;Wahlers, Jessica;Lime, Elaine;Meadows, Rebecca E.;Leslie, Kevin W.;Savin, Rhona;Bell, Fiona;Hansen, Eric;Helquist, Paul;Munday, Rachel H.;Wiest, Olaf;Norrby, Per-Ola. And the article was included in Nature Catalysis in 2019.Electric Literature of C38H32O2P2 This article mentions the following:

The development of computational tools to support organic synthesis, including the prediction of reaction pathways, optimization and selectivity, is a topic of intense current interest. Transition state force fields, derived by the quantum-guided mol. mechanics method, rapidly calculate the stereoselectivity of organic reactions accurately enough to allow predictive virtual screening. Here we describe CatVS, an automated tool for the virtual screening of substrate and ligand libraries for asym. catalysis within hours. It is shown for the OsO₄-catalyzed cis-dihydroxylation that the results from the automated set-up are indistinguishable from a manual substrate screen. Predictive computational ligand selection is demonstrated in the virtual ligand screen of a library of diphosphine ligands for the rhodium-catalyzed asym. hydrogenation of enamides. Subsequent exptl. testing verified that the most selective substrate-ligand combinations are successfully identified by the virtual screen. CatVS is therefore a promising tool to increase the efficiency of high-throughput experimentation. In the experiment, the researchers used many compounds, for example, (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) (cas: 133545-16-1Electric Literature of C38H32O2P2).

(R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) (cas: 133545-16-1) 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. Asymmetric catalytic performance is determined not only by the metal center but also by the chiral ligand selected.Electric Literature of C38H32O2P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Ring Expansion of Silacyclobutanes with Allenoates to Selectively Construct 2- or 3-(E)-Enoate-Substituted Silacyclohexenes was written by Tang, Xiaoxiao;Zhang, Yan;Tang, Yulang;Li, Yi;Zhou, Jiajing;Wang, Duyang;Gao, Lu;Su, Zhishan;Song, Zhenlei. And the article was included in ACS Catalysis in 2022.Formula: C26H28FeNP This article mentions the following:

Silacycle is one of the most essential core frameworks in Si-containing functional mols. However, the structural diversity of silacycles was largely limited due to the lack of general synthetic methods. Here, the authors report an efficient synthesis of exo-cyclic enoate-substituted silacyclohexenes by the ring expansion of silacyclobutanes with allenoates. The reaction proceeds with two regioselectivities during Si-C bond insertion. In the presence of the Pd/PR₃ catalyst, unsubstituted allenoates undergo β, γ-insertion to form a Si-Cβ bond, giving 2-(E)-enoate-substituted silacyclohexenes. In this pathway, a chiral phosphoramidite ligand was used to construct the stereogenic Si center enantioselectively. In the 2nd pathway, in the presence of the PtCl₂ catalyst, α-substituted allenoates undergo γ, β-insertion to form a Si-Cγ bond, leading to 3-(E)-enoate-substituted silacyclohexenes. The control experiments and d. functional theory calculations were performed to understand the regio- and stereochem. outcome of both Pd- and Pt-catalyzed ring expansion reactions. In the experiment, the researchers used many compounds, for example, (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2Formula: C26H28FeNP).

(R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2) 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. Asymmetric catalytic performance is determined not only by the metal center but also by the chiral ligand selected.Formula: C26H28FeNP

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Sequence of Intramolecular Carbonylation and Asymmetric Hydrogenation Reactions: Highly Regio- and Enantioselective Synthesis of Medium Ring Tricyclic Lactams was written by Lu, Shui-Ming;Alper, Howard. And the article was included in Journal of the American Chemical Society in 2008.Category: chiral-phosphine-ligands This article mentions the following:

The intramol. cyclocarbonylation reaction of (aminoaryloxy)-functionalized arylalkynes and analogs I (X = N, CH, CCl; Y = O, NMe, OCH₂, OCH₂CH₂; R¹ = H, Me, OMe, CN, CF₃, Cl, MeCO; R² = H, Me, CO₂Me; R³ = H, Cl, Me, CO₂Me) with palladium-complexed dendrimers on silica is a very effective method for the regioselective synthesis of methylene 8-, 9-, and 10-membered rings II. The heterogeneous dendritic catalysts were easily recovered by simple filtration and reused for up to 10 cycles with only a slight loss of activity. Asym. hydrogenation of the resulting unsaturated heterocycles II afforded optically active tricyclic lactams III in excellent yields and in high enantiomeric excess. This process can tolerate a wide array of functional groups, including halide, ether, nitrile, ketone, and ester. Moreover, the variation of heteroatom on the rings does not have any influence on the efficiency and enantioselectivity of the reaction. In the experiment, the researchers used many compounds, for example, (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) (cas: 77876-39-2Category: chiral-phosphine-ligands).

(2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) (cas: 77876-39-2) 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. Chiral ligands coordinate to metal centers to create an asymmetric environment around the reaction centers, which eventually affects enantioselectivity and reaction rate.Category: chiral-phosphine-ligands

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Enantioselective Synthesis of 3,3-Disubstituted Oxindoles through Pd-Catalyzed Cyanoamidation was written by Yasui, Yoshizumi;Kamisaki, Haruhi;Takemoto, Yoshiji. And the article was included in Organic Letters in 2008.Quality Control of (S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine This article mentions the following:

The first enantioselective intramol. cyanoamidation of olefins provides quick access to a variety of 3,3-disubstituted oxindoles. The combination of Pd(dba)₂, optically active phosphoramidite I, and N,N-dimethylpropylene urea (DMPU) in decalin were found to be the best conditions. In the experiment, the researchers used many compounds, for example, (S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine (cas: 134484-36-9Quality Control of (S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine).

(S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine (cas: 134484-36-9) belongs to chiral phosphine ligands. At present, the synthesis of new chiral phosphines designed specifically for nucleophilic organocatalysis remains a significant challenge. Indeed, very little research on chiral tertiary phosphine-catalyzed asymmetric reactions occurred prior to the year 2000.Quality Control of (S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Enantioselective Construction of Acyclic Quaternary Carbon Stereocenters: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Amide Enolates was written by Starkov, Pavel;Moore, Jared T.;Duquette, Douglas C.;Stoltz, Brian M.;Marek, Ilan. And the article was included in Journal of the American Chemical Society in 2017.Synthetic Route of C52H44N2O2P2 This article mentions the following:

Authors report a divergent and modular protocol for the preparation of acyclic mol. frameworks containing newly created quaternary carbon stereocenters. Central to this approach is a sequence composed of a (1) regioselective and -retentive preparation of allyloxycarbonyl-trapped fully substituted stereodefined amide enolates and of a (2) enantioselective palladium-catalyzed decarboxylative allylic alkylation reaction using a novel bisphosphine ligand. In the experiment, the researchers used many compounds, for example, N,N’-((1R,2R)-Cyclohexane-1,2-diyl)bis(2-(diphenylphosphino)-1-naphthamide) (cas: 174810-09-4Synthetic Route of C52H44N2O2P2).

N,N’-((1R,2R)-Cyclohexane-1,2-diyl)bis(2-(diphenylphosphino)-1-naphthamide) (cas: 174810-09-4) 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. Chiral ligands coordinate to metal centers to create an asymmetric environment around the reaction centers, which eventually affects enantioselectivity and reaction rate.Synthetic Route of C52H44N2O2P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

An efficient copper-aluminum hydrotalcite catalyst for asymmetric hydrosilylation of ketones at room temperature. [Erratum to document cited in CA149:246243] was written by Kantam, M. Lakshmi;Laha, Soumi;Yadav, Jagjit;Likhar, Pravin R.;Sreedhar, B.;Jha, Shailendra;Bhargava, Suresh;Udayakiran, M.;Jagadeesh, B.. And the article was included in Organic Letters in 2008.Quality Control of (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) This article mentions the following:

The Supporting Information Section contained errors in the optical rotation, concentration, H NMR chem. shift values, C NMR chem. shift values, HPLC retention times, and HPLC spectra. The corrected version of the Supporting Information is available online. In the experiment, the researchers used many compounds, for example, (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) (cas: 133545-16-1Quality Control of (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine)).

(R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) (cas: 133545-16-1) 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. Quality Control of (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis