Day: October 14, 2022

Saitoh, Akihito; Achiwa, Kazuo; Tanaka, Kiyoshi; Morimoto, Toshiaki published an article in Journal of Organic Chemistry. The title of the article was 《Versatile Chiral Bidentate Ligands Derived from α-Amino Acids: Synthetic Applications and Mechanistic Considerations in the Palladium-Mediated Asymmetric Allylic Substitutions》.HPLC of Formula: 286454-86-2 The author mentioned the following in the article:

A new class of chiral amidine-phosphine hybrid ligands which are readily accessible from the corresponding α-amino acids was developed. A versatility for construction of new ligands is desirable, by which a variety of reactions and substrates become applicable. Indeed, a variety of modifications, such as exchange reactions to other amino groups in the amidine skeleton and the production of other types of ligands, are possible using the precursor compounds Thus, novel chiral ligands which provide sterically and electronically different chiral circumstances were prepared and used for the palladium-mediated asym. allylic substitutions of both acyclic and cyclic compounds In these reactions, high levels of asym. induction were achieved for both substrates. A marked advancement of reactivity and enantioselectivity in palladium-catalyzed asym. allylations of 1,3-diphenylpropen-2-yl pivalate (14a) was attained by examination of electronic substituent effects in a new series of chiral P-N and S-N hybrid ligands. Mechanistic views concerning the enantiodiscriminating step were demonstrated, in which a good correlation between a novel Pr/Mr concept and the absolute configuration of allylation products are discussed for the prediction of enantioselecting direction. The use of ketene silyl acetals as nucleophiles was investigated and compared with the corresponding harder anionic carbon nucleophiles. The former nucleophiles afforded higher enantioselectivity in asym. allylic transformations of 14a. The experimental part of the paper was very detailed, including the reaction process of (S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine(cas: 286454-86-2HPLC of Formula: 286454-86-2)

(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.HPLC of Formula: 286454-86-2 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,Bora, Pranjal P.; Sun, Gui-Jun; Zheng, Wei-Feng; Kang, Qiang published 《Rh/Lewis Acid Catalyzed Regio-, Diastereo- and Enantioselective Addition of 2-Acyl Imidazoles with Allenes》.Chinese Journal of Chemistry published the findings.Synthetic Route of C38H28O4P2 The information in the text is summarized as follows:

A highly regio-, diastereo- and enantioselective addition of 2-acyl imidazoles or 2-acyl pyridines with allenes promoted by Rh/Lewis acid synergistically catalytic system was described. This atom economic approach led to the formation of the branched allylic alkylated products including acyclic quaternary all-carbon stereogenic centers in good yields with good to excellent diastereo- and enantioselectivities. Kinetic studies revealed that the rate-determining step in this process was the oxidative addition of Rh(I) with C-H bond. The results came from multiple reactions, including the reaction of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Synthetic Route 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.Synthetic Route of C38H28O4P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Cowan, David J.; Collins, Jon L.; Mitchell, Mark B.; Ray, John A.; Sutton, Peter W.; Sarjeant, Amy A.; Boros, Eric E. published their research in Journal of Organic Chemistry on December 20 ,2013. The article was titled 《Enzymatic- and Iridium-Catalyzed Asymmetric Synthesis of a Benzothiazepinylphosphonate Bile Acid Transporter Inhibitor》.HPLC of Formula: 1156547-61-3 The article contains the following contents:

A synthesis of the benzothiazepine phosphonic acid 3 (shown as I), employing both enzymic and transition metal catalysis, is described. The quaternary chiral center of 3 was obtained by resolution of Et (2-ethyl)norleucinate (4) with porcine liver esterase (PLE) immobilized on Sepabeads. The resulting (R)-amino acid (H2N)(HOOC)C(Bu)(Et) (5) was converted in two steps to aminosulfate (Bu)(Et)C(NH2)(CH2OSO3) (7), which was used for construction of the benzothiazepine ring. Benzophenone, 2-benzoyl-5-(bromomethyl)-4-methoxyphenyl trifluoromethanesulfonate (15), prepared in four steps from trimethylhydroquinone, 1,4-(MeO)2-2-MeC6H3 (11), enabled sequential incorporation of P (Arbuzov chem.) and S (Pd(0)-catalyzed thiol coupling) leading to mercaptan intermediate, di-Et 4-benzoyl-5-mercapto-2-methoxybenzylphosphonate (18). S-Alkylation of 18 with aminosulfate 7 followed by cyclodehydration afforded the corresponding dihydrobenzothiazepine. Ir-catalyzed asym. hydrogenation of this dihydrobenzothiazepine with the complex of [Ir(COD)2BArF] (26, BArF = [B(C6H3(CF3)2-3,5)4]) and Taniaphos ligand afforded the corresponding (3R,5R)-tetrahydrobenzothiazepine following flash chromatog. Oxidation of the tetrahydrobenzothiazepine to the corresponding sulfone and phosphonate hydrolysis completed the synthesis of 3 in 12 steps and 13% overall yield. The results came from multiple reactions, including the reaction of (1S)-1-(Dicyclohexylphosphino)-2-[(R)-[2-(dicyclohexylphosphino)phenyl](dimethylamino)methyl]ferrocene(cas: 1156547-61-3HPLC of Formula: 1156547-61-3)

(1S)-1-(Dicyclohexylphosphino)-2-[(R)-[2-(dicyclohexylphosphino)phenyl](dimethylamino)methyl]ferrocene(cas: 1156547-61-3) belongs to chiral phosphine ligands. Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates. HPLC of Formula: 1156547-61-3 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

Cadart, Timothee; Necas, David; Kaiser, Reinhard P.; Favereau, Ludovic; Cisarova, Ivana; Gyepes, Robert; Hodacova, Jana; Kalikova, Kveta; Bednarova, Lucie; Crassous, Jeanne; Kotora, Martin published their research in Chemistry – A European Journal in 2021. The article was titled 《Rhodium-Catalyzed Enantioselective Synthesis of Highly Fluorescent and CPL-Active Dispiroindeno[2,1-c]fluorenes》.Synthetic Route of C38H28O4P2 The article contains the following contents:

The enantioselective synthesis of chiral [7]-helical dispirodihydro[2,1-c]indenofluorenes (DSF-IFs) was achieved for the first time in good yields with high er values (er up to 99 : 1). The crucial step of the whole reaction sequence was the enantioselective intramol. [2+2+2] cycloaddition of tethered triynediols to indenofluorenediols, which was catalyzed by a Rh/SEGPHOS complex. Further transformations led to the corresponding DSF-IFs. The prepared helically chiral DSF-IFs combine circularly polarized luminescence (CPL) activity (glum=∼10-3) with exceptionally high fluorescence quantum yields (up to Φlum=0.97). In the part of experimental materials, we found many familiar compounds, such as (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Synthetic Route 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.Synthetic Route of C38H28O4P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

《Low-pressure Cobalt-Catalyzed Enantioselective Hydrovinylation of Vinylarenes》 was written by Movahhed, Sohajl; Westphal, Julia; Dindaroglu, Mehmet; Falk, Anna; Schmalz, Hans-Guenther. Reference of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxoleThis research focused onvinylarene ethene cobalt catalyst enantioselective regioselective hydrovinylation; alkenylarene preparation; C−C bond formation; alkenes; asymmetric catalysis; chirality; cobalt. The article conveys some information:

An efficient and practical protocol for the enantioselective cobalt-catalyzed hydrovinylation of vinylarenes with ethylene at low (1.2 bar) pressure was developed. As precatalysts, stable [L2CoCl2] complexes were employed that were activated in situ with Et2AlCl. A modular chiral TADDOL-derived phosphine-phosphite ligand was identified and that allowed the conversion of a broad spectrum of substrates including heterocyclic vinylarenes and vinylferrocene to smoothly afford the branched products with up to 99 % ee and virtually complete regioselectivity. Even polar functional groups such as OH, NH2, CN, and CO2R were tolerated. In the experiment, the researchers used many compounds, for example, (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Reference 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 aldehydesReference of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Application of 256390-47-3On May 18, 2018 ,《Direct Catalytic Asymmetric Aldol Reaction of α-Vinyl Acetamide》 appeared in Journal of Organic Chemistry. The author of the article were Takeuchi, Toshifumi; Kumagai, Naoya; Shibasaki, Masakatsu. The article conveys some information:

A direct catalytic asym. aldol addition of an α-vinyl 7-azaindoline amide to both aromatic and aliphatic aldehydes was promoted by a cooperative acid/base catalyst in a stereodivergent manner. The key structural element, a 7-azaindoline moiety, facilitated catalytic enolization, allowing for subsequent stereoselective aldol addition Enantioselective synthesis of the key intermediate of blumiolide C and kainic acid supported the synthetic utility of this protocol.(R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine](cas: 256390-47-3Application of 256390-47-3) was used in this study.

(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. Application of 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

Li, Chen-Long; Yang, Yusheng; Zhou, Yi; Yu, Zhi-Xiang published an article on January 31 ,2022. The article was titled 《A Formal [3+3+1] Reaction of Enyne-Methylenecyclopropanes through Au(I)-Catalyzed Enyne Cycloisomerization and Rh(I)-Catalyzed [6+1] Reaction of Vinylspiropentanes and CO》, and you may find the article in Asian Journal of Organic Chemistry.Electric Literature of C50H56O14P2 The information in the text is summarized as follows:

A formal [3+3+1] reaction through gold(I)-catalyzed enyne cycloisomerization of enyne-methylenecyclopropanes I (R1 = H, Me, Bn, n-Bu, 4-trifluoromethylphenyl; R2 = H, Me, Ph; R3 = H, Me; X = 2-nitrobenzenesulfonamido, benzenesulfonamido, 4-bromobenzenesulfonamido, O) and rhodium(I)-catalyzed [6+1] reaction of vinylspiropentanes II and CO has been developed to synthesize aza-6/7 bicyclic compounds, hexahydrocyclohepta[c]pyridinones III. DFT calculations reveal that four steps are involved in the [6+1] cycloaddition of vinylspiropentanes II and CO, including oxidative addition of cyclopropane to Rh, β-C elimination, CO insertion and reductive elimination. The experimental part of the paper was very detailed, including the reaction process of (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine](cas: 256390-47-3Electric Literature of C50H56O14P2)

(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. Electric Literature of C50H56O14P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

In 2016,You, Cai; Wei, Biao; Li, Xiuxiu; Yang, Yusheng; Liu, Yue; Lv, Hui; Zhang, Xumu published 《Rhodium-Catalyzed Desymmetrization by Hydroformylation of Cyclopentenes: Synthesis of Chiral Carbocyclic Nucleosides》.Angewandte Chemie, International Edition published the findings.Application In Synthesis of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole The information in the text is summarized as follows:

Excellent enantioselectivities (up to 97 % ee) and diastereoselectivities (up to >99:1 d.r.) have been achieved in the desymmetrization of cyclopentenes by catalytic hydroformylation. This novel methodol. provides an efficient and concise synthetic route to chiral cyclopentane carboxaldehydes. The key intermediate, (1S,3S)-(3-hydroxymethyl)cyclopentanol, for the synthesis of carbocyclic-ddA was obtained in three steps. In the experiment, the researchers used (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) 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.Application In Synthesis of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

In 2019,Journal of Organic Chemistry included an article by Chowdhury, Raghunath; Dubey, Akhil K.; Ghosh, Sunil K.. Product Details of 210169-54-3. The article was titled 《Ag(I)-Fesulphos-Catalyzed Enantioselective Synthesis of 3-Silylproline Derivatives》. The information in the text is summarized as follows:

An efficient catalytic asym. 1,3-dipolar cycloaddition of N-benzylidineiminoglycinate-derived azomethine ylides to β-silylmethylene malonates catalyzed by a Ag(I)-(1S)-1-[(1,1-dimethylethyl)thio]-2-(diphenylphosphino)ferrocene complex has been developed, affording fully substituted 3-silylproline derivatives with an all carbon quaternary center. The silylproline derivatives were obtained in moderate-to-good yields (up to 81%) in high diastereoselectivities and enantioselectivities (dr up to 95:5; er up to 96:4). Tamao-Fleming oxidation of selected 3-silylproline derivatives provided not only an efficient route but also the shortest route to 3-hydroxyproline derivatives, which are not accessible by direct 1,3-dipolar cycloadditions of azomethine ylide with frequently used arylidene/alkylidene malonates. The experimental process involved the reaction of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Product Details of 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.Product Details of 210169-54-3

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Cui, Jin; Oriez, Raphael; Noda, Hidetoshi; Watanabe, Takumi; Shibasaki, Masakatsu published an article in Angewandte Chemie, International Edition. The title of the article was 《Concise and Stereodivergent Approach to Chromanone Lactones through Copper-Catalyzed Asymmetric Vinylogous Addition of Siloxyfurans to 2-Ester-Substituted Chromones》.Recommanded Product: (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine] The author mentioned the following in the article:

Vicinal oxygen-containing tetra- and tri-substituted stereocenters exist widely in chromanone lactone and tetrahydroxanthone natural products. Their enantioselective construction in a single step remains elusive and poses a formidable challenge for chem. synthesis. Here, authors report the first copper(I)-catalyzed asym. vinylogous additions of siloxyfurans to 2-ester-substituted chromones, which enable concise and enantioselective assembly of chromanone lactones. Both syn and anti adducts can be accessed with excellent diastereo- and enantioselectivity by judicious choice of the chiral ligands. Authors approach allowed for the efficient synthesis of (-)-blennolide B with precise stereochem. control, which provides a formal synthesis of secalonic acid A. In addition to this study using (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine], there are many other studies that have 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]) was used in this study.

(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