Tag: 441.34

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

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

New chiral ferrocenyl P,S-ligands for highly diastereo-/enantioselective catalytic [3 + 2] cycloaddition of azomethine ylides with cyclic and acyclic enones was written by Zhang, Cheng;Yu, Sai-Bo;Hu, Xiang-Ping;Wang, Dao-Yong;Zheng, Zhuo. And the article was included in Organic Letters in 2010.Name: (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine This article mentions the following:

A new family of chiral ferrocenyl P,S-ligands I (R = Me, i-Pr, Ph, 4-ClC₆H₄, 4-MeC₆H₄, PhCH₂) has been developed and successfully applied in a highly endo-selective catalytic asym. cycloaddition of azomethine ylides with various enones, including cyclic and acyclic α-enones. For cyclic α-enones, [Cu(CH₃CN)₄]ClO₄/(R_c,S_Fc)-I (R = i-Pr) complex catalyzed the cycloaddition to give the sole endo-cycloadducts in perfect enantioselectivities (normally 99% ee), while AgOAc/(R_c,S_Fc)-I (R = i-Pr) catalytic system exhibited good endo/exo selectivities (endo/exo = 91/9 to 96/4) and high enantiocontrol (up to 98% ee) for acyclic α-enones. In the experiment, the researchers used many compounds, for example, (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2Name: (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine).

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

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Bifunctional ferrocene-based squaramide-phosphine as an organocatalyst for highly enantioselective intramolecular Morita-Baylis-Hillman reaction was written by Zhang, Xiaorui;Ma, Pengfei;Zhang, Dongxu;Lei, Yang;Zhang, Shengyong;Jiang, Ru;Chen, Weiping. And the article was included in Organic & Biomolecular Chemistry in 2014.Electric Literature of C26H28FeNP This article mentions the following:

This work demonstrates that, in accord with metal catalysis, ferrocene could be an excellent scaffold for organocatalysts. The simple and easily accessible bifunctional ferrocene-based squaramide-phosphine shows high enantioselectivity in the intramol. Morita-Baylis-Hillman reaction of 7-aryl-7-oxo-5-heptenals, giving a variety of 2-aroyl-2-cyclohexenols in up to 96% ee. In the experiment, the researchers used many compounds, for example, (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2Electric Literature of C26H28FeNP).

(R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2) belongs to chiral phosphine ligands. Generally, the efficiency of nucleophilic phosphine catalysis often depends on the nature of the tertiary phosphine. Over the last decade, however, and especially since 2005, considerable progress has been made in asymmetric phosphine catalysis.Electric Literature of C26H28FeNP

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Interactions of cationic palladium(II)- and platinum(II)-η³-allyl complexes with fluoride: is asymmetric allylic fluorination a viable reaction? was written by Hintermann, Lukas;Lang, Florian;Maire, Pascal;Togni, Antonio. And the article was included in European Journal of Inorganic Chemistry in 2006.Name: (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine This article mentions the following:

The origin of dramatic anion effect on palladium-catalyzed asym. allylic substitution, an improvement of enantioselectivity caused by fluoride additives, was explored by reacting of fluoride anions from different sources with pre-formed palladium and platinum allyl complexes. The complex cations [M(η³-RCH:CHCHR)(L₂-N,P)]⁺ (M = Pd, R = Ph, Cy; RCH:CHCHR = indenyl; M = Pt, R = Ph; L₂ = 3-tert-butyl-1-[1-[2-diphenylphosphinoferrocenyl]ethyl]-1H-pyrazole [PPFPz-3-^tBu]) were prepared as salts with PF₆^– or SbF₆^–. The cations were characterized by NMR spectroscopy in solution and by x-ray crystallog. in the solid state. Their reactions with sources of nucleophilic and “naked” fluoride were investigated by multinuclear NMR spectroscopy. The Pd allyl complexes did not undergo any nucleophilic substitution with concomitant release of allyl fluorides. The dicyclohexylallyl fragment was released as a 1,3-diene, 1-cyclohexyl-3-cyclohexylidene-1-propene, by fluoride-induced elimination, but for other allyl complexes the fluoride anions caused rather non-specific decomposition The complex [Pt(η³-1,3-Ph₂C₃H₃)(L₂-N,P)]PF₆ underwent an anion exchange with Me₄NF to give [Pt(1,3-Ph₂C₃H₃)(L₂-N,P)]F which existed as a mixture of interconverting allyl isomers in solution at ambient temperature For similar bromide salt, [Pt(η³-1,3-Ph₂C₃H₃)(L₂-N,P)]Br, allyl isomerization was slow at ambient temperature Precursors of Pt(0) reacted with 3-bromo-1,3-diphenyl-1-propene to give [Pt₂(μ-Br)₂(η³-1,3-Ph₂C₃H₃)₂] and precursors of Pd(0) underwent oxidative additions with both 3-bromo- and 3-fluoro-1,3-diphenyl-1-propenes to give 1,3-diphenylallyl complexes of Pd(II). Therefore, the nucleophilic attack of fluoride on the allyl fragment of Pd(II) complexes is endergonic and thermodynamically unfavored, and the high energy barrier of this step is difficult to overcome in a catalytic allylic fluorination reaction. In the experiment, the researchers used many compounds, for example, (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2Name: (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine).

(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. Chiral phosphine catalysts: Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates.Name: (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine

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

Iridium Catalysts with f-Amphox Ligands: Asymmetric Hydrogenation of Simple Ketones was written by Wu, Weilong;Liu, Shaodong;Duan, Meng;Tan, Xuefeng;Chen, Caiyou;Xie, Yun;Lan, Yu;Dong, Xiu-Qin;Zhang, Xumu. And the article was included in Organic Letters in 2016.COA of Formula: C26H28FeNP This article mentions the following:

A series of modular and rich electronic tridentate ferrocene aminophosphoxazoline ligands (f-amphox) have been successfully developed and used in iridium-catalytic asym. hydrogenation of simple ketones to afford corresponding enantiomerically enriched alcs. under mild conditions with superb activities and excellent enantioselectivities (up to 1,000,000 TON, almost all products up to >99% ee, full conversion). The resulting chiral alcs. and their derivatives are important intermediates in pharmaceuticals. 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. 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: C26H28FeNP

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

Synthesis, crystal structure, heat capacities and thermodynamic properties of a potential enantioselective catalyst was written by Zeng, Ju-Lan;Yu, Sai-Bo;Cao, Zhong;Yang, Dao-Wu;Sun, Li-Xian;Zhang, Ling;Zhang, Xiong-Fei. And the article was included in Journal of Thermal Analysis and Calorimetry in 2011.Application In Synthesis of (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine This article mentions the following:

A new potential enantioselective catalyst derived from ferrocene, 1-{(R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyl}benzimidazole (DPFEB), was prepared and its absolute structure was characterized by means of single crystal X-ray diffraction. The molar heat capacity of DPFEB was measured by means of temperature modulated differential scanning calorimetry over the temperature range of 200-530 K, and the thermodn. functions of [H _T – H _298.15] and [S _T – S _298.15] were calculated Further more, thermogravimetry experiment revealed that DPFEB exhibited a three step thermal decomposition process with the final residual of 28.7%. In the experiment, the researchers used many compounds, for example, (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2Application In Synthesis of (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine).

(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. Chiral ligands coordinate to metal centers to create an asymmetric environment around the reaction centers, which eventually affects enantioselectivity and reaction rate.Application In Synthesis of (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Palladium-Catalyzed Enantioselective Arylation of Racemic Ketones to Form Bridged Bicycles via Dynamic Kinetic Resolution was written by Huang, Xiaolei;Oh, William Ray Jun Jie;Zhou, Jianrong Steve. And the article was included in Angewandte Chemie, International Edition in 2018.Name: (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine This article mentions the following:

Enantioselective α-arylation of racemic ketones containing existing α’-stereocenters is reported for the first time via base-induced dynamic kinetic resolution Bridged bicyclic rings are formed in good ee values, which are difficult to obtain otherwise. Furthermore, reactions in DMSO-d₆ resulted in extensive deuteration of both α- and α’-positions in the products, thus supporting a pathway involving rapid, reversible deprotonation of ketones under catalytic conditions. In the experiment, the researchers used many compounds, for example, (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2Name: (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine).

(R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2) belongs to chiral phosphine ligands. Generally, the efficiency of nucleophilic phosphine catalysis often depends on the nature of the tertiary phosphine. Effective chiral catalysts for nucleophilic phosphine catalysis are scarce, seriously limiting the development of asymmetric variants. Name: (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis