Month: October 2022

In 2018,Angewandte Chemie, International Edition included an article by Itoh, Taisuke; Kanzaki, Yamato; Shimizu, Yohei; Kanai, Motomu. Recommanded Product: (R)-1-{(R)-2-[Bis(4-methoxy-3,5-dimethylphenyl)phosphino]ferrocenyl}-ethylbis(2-methylphenyl)phosphine. The article was titled 《Copper(I)-catalyzed enantio- and diastereodivergent borylative coupling of styrenes and imines》. The information in the text is summarized as follows:

We report copper(I)-catalyzed enantio- and diastereodivergent borylative coupling of styrenes Ar1CH:CH2 with imines RCH:HP(S)Ar22 and B2pin2 to produce enantiomerically-enriched α,β-dibranched γ-boryl amine derivatives RCH(NHPSAr22)CHAr1CH2Bpin (3). Each of the four possible stereoisomers of the products, derived from the two contiguous stereocenters, was selectively accessible by choosing a proper chiral ligand for the copper catalyst. This method, which combines catalyst-controlled stereodivergency and constitutional divergency derived from the lynchpin motif (i.e., the C-B bond), offers a strategy for addressing the construction of mol. structural diversity concomitant with precise chirality control. The results came from multiple reactions, including the reaction of (R)-1-{(R)-2-[Bis(4-methoxy-3,5-dimethylphenyl)phosphino]ferrocenyl}-ethylbis(2-methylphenyl)phosphine(cas: 849924-49-8Recommanded Product: (R)-1-{(R)-2-[Bis(4-methoxy-3,5-dimethylphenyl)phosphino]ferrocenyl}-ethylbis(2-methylphenyl)phosphine)

(R)-1-{(R)-2-[Bis(4-methoxy-3,5-dimethylphenyl)phosphino]ferrocenyl}-ethylbis(2-methylphenyl)phosphine(cas: 849924-49-8) belongs to chiral phosphine ligands. Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates. Recommanded Product: (R)-1-{(R)-2-[Bis(4-methoxy-3,5-dimethylphenyl)phosphino]ferrocenyl}-ethylbis(2-methylphenyl)phosphine 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

In 2017,Goulioukina, Nataliya S.; Shergold, Ilya A.; Rybakov, Victor B.; Beletskaya, Irina P. published 《One-Pot Two-Step Synthesis of Optically Active α-Amino Phosphonates by Palladium-Catalyzed Hydrogenation/Hydrogenolysis of α-Hydrazono Phosphonates》.Advanced Synthesis & Catalysis published the findings.Safety of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole The information in the text is summarized as follows:

An efficient and convenient 1-pot procedure for the stereoselective catalytic synthesis of ring-substituted [amino(phenyl)methyl]phosphonates was developed. The enantioselective hydrogenation of easily available diisopropyl (Z)-[aryl(phenylhydrazono)methyl]phosphonates using Pd(II) acetate as a precatalyst, (R)-2,2′-bis(diphenylphosphino)-5,5′-dichloro-6,6′-dimethoxy-1,1′-biphenyl [(R)-Cl-MeO-BIPHEP] as a ligand, and (1S)-(+)-10-camphorsulfonic acid as an activator in a mixture of 2,2,2-trifluoroethanol and CH2Cl2 at ambient temperature gave corresponding [aryl(2-phenylhydrazino)methyl]phosphonates. The subsequent cleavage of the N-N bond was accomplished with H2 after the addition of Pd on C and MeOH into crude reaction mixture to afford the optically active [amino(aryl)methyl]phosphonates. The method is operationally simple and provides an appreciable enantioselectivity up to 98% ee. The results came from multiple reactions, including the reaction of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Safety 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: 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 aldehydesSafety of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

In 2019,Journal of the American Chemical Society included an article by Hong, Feng-Lin; Wang, Ze-Shu; Wei, Dong-Dong; Zhai, Tong-Yi; Deng, Guo-Cheng; Lu, Xin; Liu, Rai-Shung; Ye, Long-Wu. Safety of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole. The article was titled 《Generation of Donor/Donor Copper Carbenes through Copper-Catalyzed Diyne Cyclization: Enantioselective and Divergent Synthesis of Chiral Polycyclic Pyrroles》. The information in the text is summarized as follows:

In the presence of Cu(MeCN)4PF6, N-propargyl vinylaryl ynamides such as I (Ts = 4-MeC6H4SO2) underwent diastereoselective cascade cyclization reactions via copper carbenes to yield cyclopropabenzoisoindoles such as II; when a nonracemic bisoxazoline ligand was used, the cyclopropabenzoisoindoles were prepared in 90:10-97:3 er. N-Propargyl aryl ynamides such as III underwent enantioselective cyclization reactions in the presence of Cu(MeCN)4PF6 and (R)- or (S)-Segphos to yield nonracemic indanopyrroles such as IV. Mechanistic studies revealed that donor/donor copper carbenes are involved in the 1,5-diyne cyclization reactions, in contrast to reactions of gold catalysts, and provides a novel method to generate donor/donor carbenes. The experimental process involved the reaction of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Safety 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: 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 aldehydesSafety of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

HPLC of Formula: 210169-54-3In 2016 ,《Asymmetric Synthesis of Protected Cyclohexenylamines and Cyclohexenols by Rhodium-Catalyzed [2+2+2] Cycloaddition》 appeared in Angewandte Chemie, International Edition. The author of the article were Masutomi, Koji; Sugiyama, Haruki; Uekusa, Hidehiro; Shibata, Yu; Tanaka, Ken. The article conveys some information:

Cationic rhodium(I)/axially chiral biaryl bis(phosphine) complexes catalyze the asym. [2+2+2] cycloaddition of 1,6-enynes with electron-rich functionalized alkenes, enamides, and vinyl carboxylates, to produce the corresponding protected cyclohexenylamines and cyclohexenols. Regioselectivity depends on structures of substrates. The present cycloaddition was successfully applied to the enantioselective total synthesis of (-)-porosadienone by using the amide moiety as a leaving group. After reading the article, we found that the author used (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3HPLC of Formula: 210169-54-3)

(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.HPLC of Formula: 210169-54-3

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Synthetic Route of C38H28O4P2In 2016 ,《Rhodium-Catalyzed Hydrocarboxylation of Olefins with Carbon Dioxide》 appeared in European Journal of Organic Chemistry. The author of the article were Kawashima, Shingo; Aikawa, Kohsuke; Mikami, Koichi. The article conveys some information:

The catalytic hydrocarboxylation of styrenes derivatives and α,β-unsaturated carbonyl compounds with CO2 (101.3 kPa) in the presence of an air-stable rhodium catalyst was explored. The combination of [RhCl(cod)]2 (cod = cyclooctadiene) as a catalyst and diethylzinc as a hydride source allowed for effective hydrocarboxylation and provided the corresponding α-aryl carboxylic acids in moderate to excellent yields. In this catalytic process with carbon dioxide, intervention of the RhI-H species, which could be generated from the RhI catalyst and diethylzinc, was clarified. Significantly, the catalytic asym. hydrocarboxylation of α,β-unsaturated esters with carbon dioxide was also performed by employing a cationic rhodium complex possessing (S)-(-)-4,4′-bi-1,3-benzodioxole-5,5′-diylbis(diphenylphosphine) [(S)-SEGPHOS] as a chiral diphosphine ligand. A plausible model for asym. induction was proposed by determination of the absolute configuration of the product.(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

《Tandem Catalytic Indolization/Enantioconvergent Substitution of Alcohols by Borrowing Hydrogen to Access Tricyclic Indoles》 was written by Yang, Guoqiang; Pan, Jiaoting; Ke, Ya-Ming; Liu, Yongbing; Zhao, Yu. Name: (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxoleThis research focused ontricyclic indole preparation enantioselective; alc alkynyl aniline tandem indolization iridium phosphoric acid catalyst; enantioselectivity; hydrogen; redox-neutral catalysis; relay catalysis; tricyclic indoles. The article conveys some information:

An efficient tandem catalysis method is achieved for the direct conversion of alc.-containing alkynyl anilines 2-H2N-5-RC6H3CC(CH2)3CH(R1)OH (R = H, Me, t-Bu, F; R1 = Bu, cyclohexylmethyl, Ph, 2-naphthyl, furan-2-yl, etc.) to valuable chiral 2,3-fused tricyclic indoles (S)-I. This method relies on a tandem indolization followed by enantioconvergent substitution of alcs. via borrowing hydrogen to construct two rings in one step, enabled by relay and cooperative catalysis of a chiral iridium complex with a chiral phosphoric acid. Highly diastereoselective transformations of the tricyclic indole products (S)-I (R = H; R1 = isobutyl) also provide efficient access to a diverse array of complex polycyclic indoline compounds, e.g., II. In the experiment, the researchers used many compounds, for example, (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Name: (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.Name: (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Recommanded Product: (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine]On September 17, 2008 ,《Intermolecular, Catalytic Asymmetric Hydroamination of Bicyclic Alkenes and Dienes in High Yield and Enantioselectivity》 was published in Journal of the American Chemical Society. The article was written by Zhou, Jianrong; Hartwig, John F.. The article contains the following contents:

A set of catalytic, intermol. hydroaminations of strained bicyclic olefins and dienes are reported that occur in both high yield and high enantioselectivity. These reactions occur with a catalyst generated from [Ir(cyclooctene)2Cl]2, sterically hindered and electron-rich derivatives of the Segphos (I, R1 = Ph, 3,5-diMeC6H3, 3,5-di-tert-butyl-4-methoxyphenyl) and BIPHEP (II R2 = R1, 3,4,5-trimethoxyphenyl) families of ligands, and a soluble base. This system catalyzes the addition of various anilines to norbornene, norbornadiene, and other bicyclic olefins. The products from addition of p-anisidine can be transformed to BOC-protected norbornylamine and to substituted cyclopentanes in nearly enantiopure form. Mechanistic studies show that addition of aniline-d2 occurs in a syn fashion and suggest that the catalytic cycle comprises oxidative addition of aniline to form a bis-anilide hydride complex, followed by migratory insertion of olefin and reductive elimination of product in a series of steps involving iridium complexes containing ancillary bisphosphine and arylamide ligands. In the experiment, the researchers used (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine](cas: 256390-47-3Recommanded Product: (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine])

(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. Recommanded Product: (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine]

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

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

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