Day: October 13, 2022

《Direct Catalytic Asymmetric Aldol Reaction of α-Alkoxyamides to α-Fluorinated Ketones》 was published in Angewandte Chemie, International Edition in 2019. These research results belong to Pluta, Roman; Kumagai, Naoya; Shibasaki, Masakatsu. Application In Synthesis of (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine] The article mentions the following:

α-Oxygen-functionalized amides found particular utility as enolate surrogates for direct aldol couplings with α-fluorinated ketones in a catalytic manner. Because of the likely involvement of open transition states, both syn- and anti-aldol adducts can be accessed with high enantioselectivity by judicious choice of the chiral ligands. A broad variety of alkoxy substituents on the amides and aryl and fluoroalkyl groups on the ketone were tolerated and the corresponding substrates delivered a range of enantioenriched fluorinated 1,2-dihydroxycarboxylic acid derivatives with divergent diastereoselectivity depending on the ligand used. The amide moiety of the aldol adduct was transformed into a variety of functional groups without protection of the tertiary alc., showcasing the synthetic utility of the present asym. aldol process. The experimental process involved the reaction of (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine](cas: 256390-47-3Application In Synthesis of (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. Application In Synthesis of (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine]

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Mato, Raquel; Manzano, Ruben; Reyes, Efraim; Carrillo, Luisa; Uria, Uxue; Vicario, Jose L. published an article in Journal of the American Chemical Society. The title of the article was 《Catalytic Enantioselective Transannular Morita-Baylis-Hillman Reaction》.Name: (S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine The author mentioned the following in the article:

Catalytic and enantioselective approaches to transannular reactions are very limited and mostly are based on chiral Lewis acid catalyzed pericyclic reactions. The authors present an efficient and straightforward methodol. to access bicyclic carbo- and heterocyclic scaffolds combining different ring sizes through transannular Morita-Baylis-Hillman reaction catalyzed by a chiral enantiopure bifunctional phosphine. The reaction is remarkably wide in scope and enables the use of a variety of medium and large size ketoenone substrates leading to the final products in high yields and providing excellent stereocontrol in the formation of a quaternary stereogenic center at the ring fusion. Moreover, its potential as a general tool in organic synthesis was highlighted through the accomplishment of the first enantioselective total synthesis of (-)-γ-gurjunene, a sesquiterpene natural product. The experimental process involved the reaction of (S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine(cas: 286454-86-2Name: (S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine)

(S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine(cas:286454-86-2) is one of aminophosphine type ligands. An increased interest in aminophosphine type ligands used for asymmetric synthesis has been witnessed.Name: (S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine 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

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