Category: chiral-phosphine-ligands

A new preparation of homochiral N-protected 5-hydroxy-3-piperidenes, promising chiral building blocks, by palladium-catalyzed deracemization of their alkyl carbonates was written by Takahata, Hiroki;Suto, Yumiko;Kato, Erina;Yoshimura, Yuichi;Ouchi, Hidekazu. And the article was included in Advanced Synthesis & Catalysis in 2007.Application of 174810-09-4 This article mentions the following:

The Pd-catalyzed deracemization of N-protected alkyl carbonates of 5-hydroxy-3-piperidenes (e.g. N-(p-tolylsulfonyl)-5-(methoxycarbonyloxy)-1,2,5,6-tetrahydropyridine) using chiral phosphine ligands is described. A Trost ligand such as (R)-BPA ((1R,2R)-1,2-bis[[2-(diphenylphosphino)benzoyl]amino]cyclohexane) is a suitable chiral ligand for the deracemization, providing N-protected 5-hydroxy-3-piperidenes in good yields with good to high enantioselectivities. A plausible mechanism for the reaction is proposed. In the experiment, the researchers used many compounds, for example, N,N’-((1R,2R)-Cyclohexane-1,2-diyl)bis(2-(diphenylphosphino)-1-naphthamide) (cas: 174810-09-4Application of 174810-09-4).

N,N’-((1R,2R)-Cyclohexane-1,2-diyl)bis(2-(diphenylphosphino)-1-naphthamide) (cas: 174810-09-4) 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. Asymmetric catalytic performance is determined not only by the metal center but also by the chiral ligand selected.Application of 174810-09-4

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Asymmetric hydrogenation of α,β-unsaturated ester-phosphonates was written by Huang, Yange;Berthiol, Florian;Stegink, Bart;Pollard, Michael M.;Minnaard, Adriaan J.. And the article was included in Advanced Synthesis & Catalysis in 2009.Application of 864529-90-8 This article mentions the following:

The Rh-catalyzed asym. hydrogenation of readily available α,β-unsaturated ester-phosphonates affords the corresponding α-chiral phosphonates in excellent yield and ee. The resulting products are useful multifunctional building blocks applied in the synthesis of physiol. active compounds 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: 864529-90-8Application of 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. 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. Application of 864529-90-8

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Stereoselective Process for a CCR3 Antagonist was written by Yue, Tai-Yuen;McLeod, Douglas D.;Albertson, Kevin B.;Beck, Steven R.;Deerberg, Joerg;Fortunak, Joseph M.;Nugent, William A.;Radesca, Lilian A.;Tang, Liya;Xiang, Cathie Dong. And the article was included in Organic Process Research & Development in 2006.Application of 77876-39-2 This article mentions the following:

A convergent, multikilogram, stereoselective synthesis of 1 is described. A key fragment, (S)-3-(4-fluorobenzyl)piperidine (2) was synthesized from valerolactam in three steps using our recently discovered Ir-BDPP-catalyzed asym. hydrogenation. Another key fragment, (1R,2R)-2-(benzyloxycarbonylamino)cyclohexanecarboxaldehyde (3) was synthesized from meso-hexahydrophthalic anhydride in seven steps. The stereochem. was set in the first step of this sequence via a quinidine-mediated desymmetrization of the meso-anhydride. Coupling of the fragments 2 and 3 followed by deprotection provided the penultimate 23. The active pharmaceutical ingredient (API) free base 1 was obtained by treatment of 23 with the aminothiazole fragment 4 under mild conditions. In the experiment, the researchers used many compounds, for example, (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) (cas: 77876-39-2Application of 77876-39-2).

(2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) (cas: 77876-39-2) belongs to chiral phosphine ligands. Generally, the efficiency of nucleophilic phosphine catalysis often depends on the nature of the tertiary phosphine. Chiral phosphine catalysts: Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates.Application of 77876-39-2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

High stereoselectivity in asymmetric Grignard cross-coupling catalyzed by nickel complexes of chiral (aminoalkylferrocenyl)phosphines was written by Hayashi, Tamio;Tajika, Masatoyo;Tamao, Kohei;Kumada, Makoto. And the article was included in Journal of the American Chemical Society in 1976.Category: chiral-phosphine-ligands This article mentions the following:

Chiral (aminoalkylferrocenyl)phosphines were effective ligands for Ni-phosphine catalyzed asym. Grignard cross-coupling reactions. In the presence of a 1:2 mixture of anhydrous NiCl2 and (S)-(R)-I (R)-(S)-I or (S)-II, the cross-coupling of PhCHMeMgCl with CH2:CHBr occurred smoothly at 0 to -20° to give 3-phenyl-1-butene of 52 ∼63% optical purity, only 4% optical yield was obtained using (R)-III as a chiral ligand. The ability of (S)-(R)-I, (R)-(S)-I and (S)-II to cause asymmetric induction was due to the complexation of the Mg atom in the Grignard reagent with the Me2N group on these (aminoalkylferrocenyl)phosphines. In the experiment, the researchers used many compounds, for example, (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2Category: chiral-phosphine-ligands).

(R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2) 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.Category: chiral-phosphine-ligands

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Copper(I) Diphosphine Bifluoride Complexes as Efficient Preactivated Catalysts for Nucleophilic Addition on Unsaturated Functional Groups was written by Rasson, Corentin;Riant, Olivier. And the article was included in Organic Process Research & Development in 2020.Reference of 37002-48-5 This article mentions the following:

Herein we report the synthesis of a family of copper(I) diphosphine bifluoride complexes, their characterization, and their use as efficient preactivated catalysts for nucleophilic copper addition of pronucleophiles on unsaturations. Their use as mechanistic probes is also highlighted by the identification of two copper deuterides. 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: 37002-48-5Reference 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. Although many reactions require more nucleophilic trialkylphosphines as catalysts, only a few chiral trialkylphosphines are available. Chiral ligands coordinate to metal centers to create an asymmetric environment around the reaction centers, which eventually affects enantioselectivity and reaction rate.Reference of 37002-48-5

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Copper-Catalyzed Regio- and Stereoselective Aminoboration of Alkenylboronates was written by Nishikawa, Daiki;Hirano, Koji;Miura, Masahiro. And the article was included in Organic Letters in 2016.Safety of (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) This article mentions the following:

A Cu-catalyzed aminoboration of alkenyl dan boronates (dan = 1,8-diaminonaphthyl) with diboron reagents and hydroxylamines was developed. The reaction proceeds regio- and stereoselectively to form the corresponding β-boryl-α-aminoboronic acid derivatives of potent interest in medicinal chem. Addnl., the ligand-controlled syn/anti diastereoselectivity switching and preliminary asym. catalysis are 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. 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. Most of these phosphines are acyclic, usually possess low nucleophilic activity, and generally display poor enantioselectivities for phosphine organocatalysis. Safety of (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Palladium-Catalyzed Asymmetric Direct Intermolecular Allylation of α-Aryl Cyclic Vinylogous Esters: Divergent Synthesis of (+)-Oxomaritidine and (-)-Mesembrine was written by Wang, Wei;Dai, Jun;Yang, Qiqiong;Deng, Yu-Hua;Peng, Fangzhi;Shao, Zhihui. And the article was included in Organic Letters in 2021.Application of 174810-09-4 This article mentions the following:

We demonstrate that α-aryl cyclic vinylogous esters are competent substrates in the direct intermol. Pd-catalyzed asym. allylic alkylation, enabling a straightforward enantioselective synthesis of 6-allyl-6-aryl-3-ethoxycyclohex-2-en-1-ones, common motifs embedded in numerous structurally diverse natural products. As an initial demonstration of the utility of this protocol, the first catalytic enantioselective total synthesis of (+)-oxomaritidine and an improved five-step catalytic enantioselective synthesis of (-)-mesembrine have been completed divergently. In the experiment, the researchers used many compounds, for example, N,N’-((1R,2R)-Cyclohexane-1,2-diyl)bis(2-(diphenylphosphino)-1-naphthamide) (cas: 174810-09-4Application of 174810-09-4).

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. Most of these phosphines are acyclic, usually possess low nucleophilic activity, and generally display poor enantioselectivities for phosphine organocatalysis. Application of 174810-09-4

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Diastereoselective synthesis of an argatroban intermediate, ethyl (2R,4R)-4-methylpipecolate, by means of a Mandyphos/rhodium complex-catalyzed hydrogenation was written by Ferraboschi, Patrizia;De Mieri, Maria;Grisenti, Paride;Lotz, Matthias;Nettekoven, Ulrike. And the article was included in Tetrahedron: Asymmetry in 2011.Reference of 133545-16-1 This article mentions the following:

The synthetic antithrombotic argatroban is a dipeptide between the nonproteinogenic (2R,4R)-4-methyl-2-piperidine carboxylic acid and L-arginine, in turn bonded to a methyltetrahydroquinoline sulfonyl group. An extensive screening of transition metal-based complexes with different ligands was performed in order to identify the best catalyst for the diastereoselective hydrogenation of a suitable 4,5-dehydropiperidine precursor aimed toward a synthesis of the (2R,4R)-4-Me piperidine moiety. 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. Chiral phosphine catalysts: Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates.Reference of 133545-16-1

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Mechanistic and asymmetric investigations of the Au-catalysed cross-coupling between aryldiazonium salts and arylboronic acids using (P,N) gold complexes was written by Tabey, Alexis;Berlande, Murielle;Hermange, Philippe;Fouquet, Eric. And the article was included in Chemical Communications (Cambridge, United Kingdom) in 2018.Formula: C26H28FeNP This article mentions the following:

To explore the different mechanisms possibly occurring in the Au-catalyzed cross-coupling of ArN₂BF₄ and ArB(OH)₂ in the presence of CsF, various stoichiometric experiments were performed on Au complexes with (P,N) ligands. Employing 2-pyridylphenyl-diphenylphosphine allowed the authors to suggest three different mechanistic pathways, starting either with a transmetalation step, via two consecutive single electron transfers, or by implying a transmetalation between Au(I) and Au(III) species. Moreover, when using com. available chiral (P,N) ligands, the asym. formation of atropoisomeric biaryls from suitable aryldiazonium salts and arylboronic acids could be achieved with e.e. up to 26%. 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. At present, the synthesis of new chiral phosphines designed specifically for nucleophilic organocatalysis remains a significant challenge. Most of these phosphines are acyclic, usually possess low nucleophilic activity, and generally display poor enantioselectivities for phosphine organocatalysis. Formula: C26H28FeNP

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Rhodium-Catalyzed Highly Diastereo- and Enantioselective Synthesis of a Configurationally Stable S-Shaped Double Helicene-Like Molecule was written by Kinoshita, Suzuka;Yamano, Ryota;Shibata, Yu;Tanaka, Yusuke;Hanada, Kyoichi;Matsumoto, Takashi;Miyamoto, Kazunori;Muranaka, Atsuya;Uchiyama, Masanobu;Tanaka, Ken. And the article was included in Angewandte Chemie, International Edition in 2020.Recommanded Product: (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) This article mentions the following:

An S-shaped double helicene-like mol. (>99% ee), possessing stable helical chirality, has been synthesized by the rhodium(I)/difluorphos complex-catalyzed highly diastereo- and enantioselective intramol. double [2+2+2] cycloaddition of a 2-naphthol- and benzene-linked hexayne. The collision between two terminal naphthalene rings destabilizes the helical chirality of the S-shaped double helicene-like mol., but the introduction of two addnl. fused benzene rings significantly increases the configurational stability. Thus, no epimerization and racemization were observed even at 100°C. The enantiopure S-shaped double helicene-like mol. forms a trimer through the multiple C-H…π and C-H…O interactions in the solid-state. The trimers stack to form columnar packing structures, in which neighboring stacks have opposite dipole directions. The accumulation of helical structures in the same direction in the S-shaped double helicene-like mol. enhanced the chiroptical properties. In the experiment, the researchers used many compounds, for example, (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) (cas: 133545-16-1Recommanded Product: (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. The synthesis of novel trialkylphosphines can be quite difficult, thereby limiting the scope of their chiral variants. Chiral ligands coordinate to metal centers to create an asymmetric environment around the reaction centers, which eventually affects enantioselectivity and reaction rate.Recommanded Product: (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis