Category: chiral-phosphine-ligands

In 2010,Angewandte Chemie, International Edition included an article by Landert, Heidi; Spindler, Felix; Wyss, Adrian; Blaser, Hans-Ulrich; Pugin, Benoit; Ribourduoille, Yann; Gschwend, Bjoern; Ramalingam, Balamurugan; Pfaltz, Andreas. Reference of (R)-1-[(R)-1-(Di-tert-butylphosphino)ethyl]-2-[(R)-phenylphosphinoyl]ferrocene. The article was titled 《Chiral Mixed Secondary Phosphine-Oxide-Phosphines: High-Performing and Easily Accessible Ligands for Asymmetric Hydrogenation》. The information in the text is summarized as follows:

Combining secondary phosphine oxides (SPOs) with phosphines leads to highly effective chiral bidentate ligands for transition-metal-based catalysts. The authors present results for selected members of two SPO-P ligand families based on a chiral ferrocenyl backbone (JoSPOphos) and a menthyl substituent (TerSPOphos), resp. JoSPOphos and TerSPOphos are readily accessible from inexpensive starting materials. The steric and electronic properties of these modular ligands can be easily tuned. In the asym. hydrogenation of functionalized alkenes, their rhodium complexes reacted to give enantioselectivities of up to 99% ee and turnover frequencies of up to 20000 h-1. In the part of experimental materials, we found many familiar compounds, such as (R)-1-[(R)-1-(Di-tert-butylphosphino)ethyl]-2-[(R)-phenylphosphinoyl]ferrocene(cas: 1221746-56-0Reference of (R)-1-[(R)-1-(Di-tert-butylphosphino)ethyl]-2-[(R)-phenylphosphinoyl]ferrocene)

(R)-1-[(R)-1-(Di-tert-butylphosphino)ethyl]-2-[(R)-phenylphosphinoyl]ferrocene(cas: 1221746-56-0) belongs to chiral phosphine ligands. Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates. Reference of (R)-1-[(R)-1-(Di-tert-butylphosphino)ethyl]-2-[(R)-phenylphosphinoyl]ferrocene These intermediates are formed through nucleophilic attack of the phosphine catalysts at electron-poor nuclei (normally carbon atoms) and then proceed through several steps to form new chemical bonds.

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

《Enantioselective Synthesis of Planar Chiral Zigzag-Type Cyclophenylene Belts by Rhodium-Catalyzed Alkyne Cyclotrimerization》 was written by Nogami, Juntaro; Tanaka, Yusuke; Sugiyama, Haruki; Uekusa, Hidehiro; Muranaka, Atsuya; Uchiyama, Masanobu; Tanaka, Ken. Computed Properties of C38H28O4P2This research focused onzigzag cyclophenylene belt enantioselective preparation; rhodium catalyst enantioselective cyclotrimerization heptynyl oxypropynylphenoxyphenylene oligomer; mol crystal structure racemic zigzag cyclophenylene belt; mechanism enantioselectivity cyclotrimerization heptynyl oxypropynylphenoxyphenylene; ring strain calculated zigzag cyclophenylene belt; fluorescence UV visible absorption zigzag cyclophenylene belt; dissymetry factor ECD CPL nonracemic zigzag cyclophenylene belt. The article conveys some information:

Planar chiral zigzag-type [8] and [12]cyclophenylene belts were prepared enantioselectively by rhodium-catalyzed enantioselective intramol. sequential cyclotrimerizations of a cyclic [oxypropynylbis(heptynyloxy)phenoxybis(heptynyl)phenylene] dimer and trimer. The observed enantioselectivity likely arose from the regioselective formation of a rhodacyclic intermediate from an unsym. triyne unit. The structure of the racemic zigzag [8]cyclophenylene belt was determined by X-ray crystallog.; the homochiral belts mesh with one another to form columns in the solid state, with columns of alternating chiralities. The ring strain of the zigzag [8]cyclophenylene belt was smaller than that of the corresponding armchair-type cycloparaphenylene despite its smaller ring size because of the presence of strain-relieving m-terphenyl moieties. The effect of the number of the benzene rings in the zigzag cyclophenylene belts on their UV/visible absorption and fluorescence was small because of the interruption of conjugation by the m-phenylene moieties, but the effect of bending on the absorption and emission peaks and on the absolute fluorescence quantum yield was significant. Modest anisotropy dissymmetry factors of the electronic CD and CPL spectra were observed for the zigzag [8]cyclophenylene belt. The results came from multiple reactions, including the reaction of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Computed Properties of C38H28O4P2)

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) may be used for: regio- and stereoselective preparation of axially chiral arylnaphthalene derivatives via rhodium-catalyzed [2+2+2] cycloaddition of diynes with naphthalenepropynoic acid derivatives or diastereo- and enantioselective hydrogenation of α-amino-β-keto ester hydrochlorides catalyzed by an iridium complex.Computed Properties of C38H28O4P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Application In Synthesis of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxoleIn 2021 ,《Computational and Experimental Insights into Asymmetric Rh-Catalyzed Hydrocarboxylation with CO2》 was published in European Journal of Organic Chemistry. The article was written by Pavlovic, Ljiljana; Pettersen, Martin; Gevorgyan, Ashot; Vaitla, Janakiram; Bayer, Annette; Hopmann, Kathrin H.. The article contains the following contents:

The asym. Rh-catalyzed hydrocarboxylation of α,β-unsaturated carbonyl compounds was originally developed by Mikami and co-workers but gives only moderate enantiomeric excesses. In order to understand the factors controlling the enantioselectivity and to propose novel ligands for this reaction, we have used computational and exptl. methods to study the Rh-catalyzed hydrocarboxylation with different bidentate ligands. The anal. of the C-CO2 bond formation transition states with DFT methods shows a preference for outer-sphere CO2 insertion, where CO2 can undergo a backside or frontside reaction with the nucleophile. The two ligands that prefer a frontside reaction, StackPhos and tBu-BOX, display an intriguing stacking interaction between CO2 and an N-heterocyclic ring of the ligand (imidazole or oxazoline). Our exptl. results support the computationally predicted low enantiomeric excesses and highlight the difficulty in developing a highly selective version of this reaction. The experimental part of the paper was very detailed, including the reaction process of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Application In Synthesis of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole)

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) is a chelating ligand used to prepare coordination complex catalysts, such as its use in Pd catalysts for the enantioselective synthesis of spiro- or benzofused hetereocycles with exocyclic olefins via enantioselective intramolecular dearomative Heck reaction of indoles, benzofurans, pyrroles and furans.Application In Synthesis of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

In 2022,Zhu, Jian-Xiang; Chen, Zhi-Chao; Du, Wei; Chen, Ying-Chun published an article in Angewandte Chemie, International Edition. The title of the article was 《Asymmetric Auto-Tandem Palladium Catalysis for 2,4-Dienyl Carbonates: Ligand-Controlled Divergent Synthesis》.COA of Formula: C38H28O4P2 The author mentioned the following in the article:

Herein a palladium-catalyzed auto-tandem reaction between 2,4-dienyl carbonates and o-TsNH arylimines or trifluoroacetophenones was presented, that proceeded through a consecutive N-allylation, vinylogous addition, π-σ-π isomerization, and another N-allylation sequence. Importantly, switchable diastereodivergent synthesis could be achieved by tuning the chiral bisphosphine ligands, which led to the construction of a broad spectrum of fused tetrahydroquinoline architectures such as I [R1 = H, 4-Me, 5-Cl, etc.; R2 = Ms, Ts, SO2(2-thienyl); R3 = Me, Ph, 2-furyl, etc.] with moderate to excellent enantioselectivity. Ligand control even enabled effective access to regiodivergent azetidines or chemodivergent β-H elimination with fair enantioselectivity, further showing the versatility of the current auto-tandem catalysis.(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3COA of Formula: C38H28O4P2) was used in this study.

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) may be used for: regio- and stereoselective preparation of axially chiral arylnaphthalene derivatives via rhodium-catalyzed [2+2+2] cycloaddition of diynes with naphthalenepropynoic acid derivatives or diastereo- and enantioselective hydrogenation of α-amino-β-keto ester hydrochlorides catalyzed by an iridium complex.COA of Formula: C38H28O4P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Bernardo, Olaya; Gonzalez-Pelayo, Silvia; Fernandez, Israel; Lopez, Luis A. published an article in 2021. The article was titled 《Gold-Catalyzed Reaction of Propargyl Esters and Alkynylsilanes: Synthesis of Vinylallene Derivatives through a Twofold 1,2-Rearrangement》, and you may find the article in Angewandte Chemie, International Edition.Category: chiral-phosphine-ligands The information in the text is summarized as follows:

The reaction of propargyl esters with alkynylsilanes under gold catalysis provides vinylallene derivatives through consecutive [1,2]-acyloxy/[1,2]-silyl rearrangements. Good yields, full atom-economy, broad substrate scope, easy scale-up and low catalyst loadings are salient features of this novel transformation. D. Functional Theory (DFT) calculations suggest a reaction mechanism involving initial [1,2]-acyloxy rearrangement to generate a gold vinylcarbene intermediate which upon regioselective attack of the alkynylsilane affords a vinyl cation which undergoes a type II-dyotropic rearrangement involving the silyl group and the metal fragment. Preliminary results on the enantioselective version of this transformation are also disclosed. The results came from multiple reactions, including the reaction of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Category: chiral-phosphine-ligands)

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) is a chelating ligand used to prepare coordination complex catalysts, such as its use in Pd catalysts for the enantioselective synthesis of spiro- or benzofused hetereocycles with exocyclic olefins via enantioselective intramolecular dearomative Heck reaction of indoles, benzofurans, pyrroles and furans.Category: chiral-phosphine-ligands

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis