Category: chiral-phosphine-ligands

The author of 《Regioconvergent and Enantioselective Rhodium-Catalyzed Hydroamination of Internal and Terminal Alkynes: A Highly Flexible Access to Chiral Pyrazoles》 were Haydl, Alexander M.; Hilpert, Lukas J.; Breit, Bernhard. And the article was published in Chemistry – A European Journal in 2016. Quality Control of (R)-1-[(R)-1-(Di-tert-butylphosphino)ethyl]-2-[(R)-phenylphosphinoyl]ferrocene The author mentioned the following in the article:

In the presence of (cyclooctadiene)rhodium(I) chloride dimer, a nonracemic ferrocenyldiphosphine monoxide, and pyridine p-toluenesulfonate (PPTS), 1-aryl-1-propynes such as RCCMe (R = Ph, 4-MeC6H4, 4-F3CC6H4, 4-PhC6H4, 2-naphthyl, 4-FC6H4, 4-ClC6H4, 4-BrC6H4, 4-MeCOC6H4, 4-O2NC6H4, PinB; PinB = 4,4,5,5-tetramethyl-1,3-dioxo-2-borolan-2-yl), phenylallene, and selected 1-aryl-2-propynes underwent chemoselective, regioselective, and enantioselective addition reactions with 1H-pyrazoles to yield nonracemic N1-allylic pyrazoles such as I (R = Ph, 4-MeC6H4, 4-F3CC6H4, 4-PhC6H4, 2-naphthyl, 4-FC6H4, 4-ClC6H4, 4-BrC6H4, 4-MeCOC6H4, 4-O2NC6H4, PinB) in 65-97% yields, in 68:32->99:1 regioselectivities, and in 80:20-97.5:2.5 er (or, for nonracemic pyrazoles, 82:18 or 85:15 dr). The method tolerated a variety of functional groups in the alkyne and pyrazole components. The structure of a phenylallylated stanozolol was determined by X-ray crystallog. In the experimental materials used by the author, we found (R)-1-[(R)-1-(Di-tert-butylphosphino)ethyl]-2-[(R)-phenylphosphinoyl]ferrocene(cas: 1221746-56-0Quality Control 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. 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. Quality Control of (R)-1-[(R)-1-(Di-tert-butylphosphino)ethyl]-2-[(R)-phenylphosphinoyl]ferrocene

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

《Asymmetric Nitrone Synthesis via Ligand-Enabled Copper-Catalyzed Cope-Type Hydroamination of Cyclopropene with Oxime》 was written by Li, Zhanyu; Zhao, Jinbo; Sun, Baozhen; Zhou, Tingting; Liu, Mingzhu; Liu, Shuang; Zhang, Mengru; Zhang, Qian. Category: chiral-phosphine-ligands And the article was included in Journal of the American Chemical Society on August 30 ,2017. The article conveys some information:

We report realization of the first enantioselective Cope-type hydroamination of oximes for asym. nitrone synthesis. The ligand promoted asym. cyclopropene “”hydronitronylation”” process employs a Cu-based catalytic system and readily available starting materials, operates under mild conditions and displays broad scope and exceptionally high enantio- and diastereocontrol. Preliminary mechanistic studies corroborate a CuI-catalytic profile featuring an olefin metalla-retro-Cope aminocupration process as the key C-N bond forming event. This conceptually novel reactivity enables the first example of highly enantioselective catalytic nitrone formation process and will likely spur further developments that may significantly expedite chiral nitrone synthesis. After reading the article, we found that the author used (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine](cas: 256390-47-3Category: chiral-phosphine-ligands)

(R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine](cas: 256390-47-3) belongs to chiral phosphine ligands. Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates. 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. Category: chiral-phosphine-ligands

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Quality Control of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxoleIn 2017 ,《Rhodium-catalyzed hydroformylation in γ-valerolactone as a biomass-derived solvent》 was published in Journal of Organometallic Chemistry. The article was written by Pongracz, Peter; Bartal, Brigitta; Kollar, Laszlo; Mika, Laszlo T.. The article contains the following contents:

Rhodium-catalyzed hydroformylation of styrene, α-methylstyrene, di-Me itaconate, and (R)-limonene was performed in gamma-valerolactone (GVL) as a proposed biomass-based environmentally benign solvent for hydroformylation referring to toluene as a generally used conventional solvent. Both achiral (triphenylphosphine, 1,3-bis(diphenylphoshino)propane) and enantiopure bidentate phosphine ligands ((S,S)-BDPP, (R)-BINAP, (R)-QUINAP, (R,R)-DIOP, (Rc),(Sp)-JOSIPHOS, (S)-SEGPHOS, (S)-(DM)-SEGPHOS) were investigated in in situ generated Rh-diphosphine catalyst systems. In general, the catalysts’ activity in GVL was lower than in toluene; however, remarkable chemo- (>99%) and regioselectivities (>95%) were achieved in GVL under identical conditions. The BDPP-modified Rh-catalyst was recycled for three consecutive cycles; however a decrease in its activity was detected. In the experiment, the researchers used many compounds, for example, (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Quality Control 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) 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.Quality Control of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

In 2018,Gupta, Naveen; Tak, Rajkumar; Nazish, Mohd; Jakhar, Ajay; Khan, Noor-ul H.; Kureshy, Rukhsana I. published 《Copper(II) Triflate Catalyzed Regioselective and Enantioselective Propargylation of Isatin Derivatives by Using Allenylboronic Acid Pinacol Ester》.European Journal of Organic Chemistry published the findings.COA of Formula: C38H28O4P2 The information in the text is summarized as follows:

The authors report a simple protocol for the synthesis of homopropargyl alcs. with isatin derivatives under milder conditions for the first time. The excellent regioselectivity and yields were observed with copper triflate as a Lewis-acid catalyst and allenylboronic acid pinacol ester as a nucleophile in aqueous media. A gram-scale synthesis was done to check the efficiency of the protocol with retention in selectivity. Further one-step functionalization of these homopropargyl alcs. was established as the synthetic application of these alkynes. The enantioselective synthesis of these chiral propargyl alcs. also was explored for the first time with an enantiomeric ratio up to 12:88. In the experiment, the researchers used many compounds, for example, (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3COA of Formula: C38H28O4P2)

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) may be used for: rhodium-catalyzed asymmetric formal olefination or cycloaddition of 1,3-dicarbonyl compounds with 1,6-diynes or 1,6-enynes, stereoselective preparation of homoallylic alcohols via Ir-catalyzed stereoselective transfer hydrogenative crotylation of an allylic acetate with alcohols or aldehydesCOA of Formula: C38H28O4P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

In 2017,Zhou, Huan; Liu, Yuan; Yang, Suhua; Zhou, Le; Chang, Mingxin published 《One-Pot N-Deprotection and Catalytic Intramolecular Asymmetric Reductive Amination for the Synthesis of Tetrahydroisoquinolines》.Angewandte Chemie, International Edition published the findings.Application of 210169-54-3 The information in the text is summarized as follows:

A one-pot N-Boc deprotection and catalytic intramol. reductive amination protocol for the preparation of enantiomerically pure tetrahydroisoquinoline alkaloids is described. The iodine-bridged dimeric iridium complexes displayed superb stereoselectivity to give tetrahydroisoquinolines, including several key pharmaceutical drug intermediates, in excellent yields under mild reaction conditions. Three additives played important roles in this reaction: titanium(IV) isopropoxide and mol. iodine accelerated the transformation of the intermediate imine to the tetrahydroisoquinoline product; p-toluenesulfonic acid contributed to the stereocontrol.(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Application of 210169-54-3) was used in this study.

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) may be used for: rhodium-catalyzed asymmetric formal olefination or cycloaddition of 1,3-dicarbonyl compounds with 1,6-diynes or 1,6-enynes, stereoselective preparation of homoallylic alcohols via Ir-catalyzed stereoselective transfer hydrogenative crotylation of an allylic acetate with alcohols or aldehydesApplication of 210169-54-3

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Zhang, Jiacheng; Huo, Xiaohong; Xiao, Junzhe; Zhao, Ling; Ma, Shengming; Zhang, Wanbin published their research in Journal of the American Chemical Society in 2021. The article was titled 《Enantio- and Diastereodivergent Construction of 1,3-Nonadjacent Stereocenters Bearing Axial and Central Chirality through Synergistic Pd/Cu Catalysis》.Computed Properties of C38H28O4P2 The article contains the following contents:

Herein, an enantio- and diastereodivergent construction of 1,3-nonadjacent stereocenters bearing allenyl axial and central chirality through synergistic Pd/Cu-catalyzed dynamic kinetic asym. allenylation with racemic allenylic esters was reported. The protocol was suitable for a wide range of substrates including the challenging allenylic esters with less sterically bulky substituents and provided chiral allenylic products I [R = n-Bu, Ph, CMe2OTBS, etc.; Ar = Ph, 2-naphthyl, 2-furyl, etc.; stereo = R or S] bearing 1,3-nonadjacent stereocenters with high levels of enantio- and diastereoselectivities (up to >20:1 dr and >99% ee). Furthermore, several representative transformations involving axial-to-central chirality transfer were conducted, affording useful structural motifs containing nonadjacent stereocenters in a diastereodivergent manner. In the experiment, the researchers used (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) 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.Computed Properties of C38H28O4P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

In 2018,Trost, Barry M.; Bai, Wen-Ju; Stivala, Craig E.; Hohn, Christoph; Poock, Caroline; Heinrich, Marc; Xu, Shiyan; Rey, Jullien published 《Enantioselective Synthesis of des-Epoxy-Amphidinolide N》.Journal of the American Chemical Society published the findings.Synthetic Route of C38H28O4P2 The information in the text is summarized as follows:

The synthesis of des-epoxy-amphidinolide N (I) was achieved in 22 longest linear and 33 total steps. Three generations of synthetic endeavors are reported herein. During the first generation, our key stitching strategy that highlighted an intramol. Ru-catalyzed alkene-alkyne (Ru AA) coupling and a late-stage epoxidation proved successful, but the installation of the α,α’-dihydroxyl ketone motif employing a dihydroxylation method was problematic. Our second generation of synthetic efforts addressed the scalability problem of the southern fragment synthesis and significantly improved the efficiency of the atom-economical Ru AA coupling, but suffered from several protecting group-based issues that proved insurmountable. Finally, relying on a judicious protecting group strategy together with concise fragment preparation, des-epoxy-amphidinolide N was achieved in a convergent fashion. Calculations disclose a hydrogen-bonding bridge within amphidinolide N. Comparisons of 13C NMR chem. shift differences using our synthetic des-epoxy-amphidinolide N suggest that amphidinolide N and carbenolide I are probably identical. In addition to this study using (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole, there are many other studies that have used (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Synthetic Route of C38H28O4P2) was used in this study.

(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.Synthetic Route of C38H28O4P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Shen, Zengming; Dornan, Peter K.; Khan, Hasan A.; Woo, Tom K.; Dong, Vy M. published an article on January 28 ,2009. The article was titled 《Mechanistic insights into the rhodium-catalyzed intramolecular ketone hydroacylation》, and you may find the article in Journal of the American Chemical Society.SDS of cas: 256390-47-3 The information in the text is summarized as follows:

Rhodium diphosphine catalysts, [Rh(dppp)2]BF4 and [Rh((R)-DTBM-SEGPHOS)]BF4 [dppp = 1,3-bis(diphenylphosphino)propane, DTBM-SEGPHOS = (4R)-[4,4′-bi-1,3-benzodioxole]-5,5′-bis(diarylphosphine), aryl = 3,5-di-tert-butyl-4-methoxyphenyl] exhibit high catalytic activity, chemo- and enantioselectivity in intramol. ketone group hydroacylation of oxo-substituted salicylaldehyde ethers, 2-RCOCHR1OC6H4CHO (1a-o), yielding 3-R-2,3-dihydro-1,4-benzodioxepin-5-ones I (2a-o; R1 = H, R = Ph, 4-CF3C6H4, 4-MeO2CC6H4, 4-ClC6H4, 4-FC6H4, 4-MeC6H4, 4-MeOC6H4, 2-naphthyl, Bu, iPr, tBu, PhCH2, Me, 2-furyl, 2-thienyl; rac-2p, R1 = R = Me; rac-2q, R1 = R = Ph). The reaction catalyzed by [Rh((R)-DTBM-SEGPHOS)]BF4 afforded seven-membered lactones 2a-o in large enantiomeric excess. A combined exptl. and theor. study aimed to elucidate the mechanism and origin of selectivity in this C-H bond activation process, is presented. Evidence is presented for a mechanistic pathway involving three key steps: (1) rhodium(I) oxidative addition into the aldehyde C-H bond, (2) insertion of the ketone C:O double bond into the rhodium hydride, and (3) C-O bond-forming reductive elimination. Kinetic isotope effects and Hammett plots support that ketone insertion is the turnover-limiting step. Detailed kinetic experiments were performed using both dppp and (R)-DTBM-SEGPHOS as ligands. With dppp, the keto-aldehyde substrate assists in dissociating a dimeric precatalyst [Rh2(μ-η6:κP,κP’-dppp)2][BF4]2 (8) and binds an active monomeric form of the catalyst. With [Rh((R)-DTBM-SEGPHOS)]BF4, there is no induction period and both substrate and product inhibition are observed In addition, competitive decarbonylation produces a catalytically inactive rhodium carbonyl species that accumulates over the course of the reaction. Both mechanisms were modeled with a kinetics simulation program, and the models were consistent with the exptl. data. D. functional theory calculations were performed to understand more elusive details of this transformation. These simulations support that the ketone insertion step has the highest energy transition state and reveal an unexpected interaction between the carbonyl-oxygen lone pair and a Rh d-orbital in this transition state structure. Finally, a model based on the calculated transition-state geometry is proposed to rationalize the absolute sense of enantioinduction observed using (R)-DTBM-SEGPHOS as the chiral ligand. In the experimental materials used by the author, we found (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine](cas: 256390-47-3SDS of cas: 256390-47-3)

(R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine](cas: 256390-47-3) belongs to chiral phosphine ligands. Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates. SDS of cas: 256390-47-3 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

Bandini, Marco; Melloni, Alfonso; Piccinelli, Fabio; Sinisi, Riccardo; Tommasi, Simona; Umani-Ronchi, Achille published an article on February 8 ,2006. The article was titled 《Highly Enantioselective Synthesis of Tetrahydro-β-Carbolines and Tetrahydro-γ-Carbolines Via Pd-Catalyzed Intramolecular Allylic Alkylation》, and you may find the article in Journal of the American Chemical Society.COA of Formula: C58H42N2O2P2 The information in the text is summarized as follows:

(2-Indolylmethylamino) or (3-indolylmethylamino)butadienyl carbonates such as I and a (pyrrolylmethylamino)butadienyl carbonate undergo enantioselective intramol. allylic alkylation reactions in the presence of tris(dibenzylideneacetone)palladium and nonracemic (diphenylphosphinobenzoyl)diamines such as II to yield nonracemic tetrahydro-β-carbolines, tetrahydro-γ-carbolines, and a pyrrolopyridine such as III (R = PhCH2) and IV (R = PhCH2) in 82-97% ee. (indolylmethylamino)butadienyl or (pyrrolylmethylamino)butadienyl carbonates such as I are prepared from indolecarboxaldehydes by imine formation and reduction, alkylation of the amines with bromobutenoate esters (or a bromobutenal), reduction of the ester or aldehyde with diisobutylaluminum hydride, and acylation with Me chlorocarbonate. A variety of ligands for the cyclocondensation are tried; diphenylphosphinobenzamides such as II give carbolines with the highest regioselectivities and enantioselectivities of the ligands tried. (indolylmethylamino)butadienyl carbonates substituted either on the indole or the butenyl moieties yield carbolines with similar enantio- and regioselectivities. An (E)-3-indolylmethylaminobutenol carbonate undergoes regio- and enantioselective allylic alkylation to yield a γ-carboline in 90% yield and 93% yield, while intramol. allylic alkylation of the corresponding (Z)-3-indolylmethylaminobutenol carbonate yields the opposite enantiomer in 65% yield and in 5% ee. The absolute configuration of III (R = PhCH2) is determined by X-ray crystallog. anal. of a β-carboline (-)-camphorsulfonamide derived from its enantiomer [the minor stereoisomer generated in the allylic alkylation which yields III (R = PhCH2)].(S)-N,N’-(1,1′-Binaphthalene]-2,2′-diyl)bis(2-diphenylphosphinobenzamide)(cas: 879505-38-1COA of Formula: C58H42N2O2P2) was used in this study.

(S)-N,N’-(1,1′-Binaphthalene]-2,2′-diyl)bis(2-diphenylphosphinobenzamide)(cas: 879505-38-1) belongs to chiral phosphine ligands. Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates. 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. COA of Formula: C58H42N2O2P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

COA of Formula: C22H22NPOn November 30, 2007 ,《Highly enantioselective synthesis of α-hydroxy phosphonic acid derivatives by Rh-catalyzed asymmetric hydrogenation with phosphine-phosphoramidite ligands》 appeared in Angewandte Chemie, International Edition. The author of the article were Wang, Dao-Yong; Hu, Xiang-Ping; Huang, Jia-Di; Deng, Jun; Yu, Sai-bo; Duan, Zheng-Chao; Xu, Xue-Feng; Zheng, Zhuo. The article conveys some information:

Unsym. hybrid phosphine-phosphoramidite ligands, e.g. PhCH2CH(OBz)P(O)(OMe)2, with central and axial chirality are applied to the highly enantioselective hydrogenation of various enol ester phosphonates, e.g. PhCH:C(OBz)P(O)(OMe)2. Enantioselectivities up to 99.9% ee are obtained for all classes of β-aryl, β-alkoxy, and β-alkyl substrates. In the experiment, the researchers used (R)-8-(Diphenylphosphino)-1,2,3,4-tetrahydronaphthalen-1-amine(cas: 960128-64-7COA of Formula: C22H22NP)

(R)-8-(Diphenylphosphino)-1,2,3,4-tetrahydronaphthalen-1-amine(cas:960128-64-7) is one of aminophosphine type ligands. An increased interest in aminophosphine type ligands used for asymmetric synthesis has been witnessed.COA of Formula: C22H22NP This growth in popularity of aminophosphine ligands in asymmetric synthesis is in part due to the growing number of convenient synthetic pathways leading to useful ligand sets.

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis