Category: chiral-phosphine-ligands

《Palladium-catalysed intramolecular asymmetric cyclohydroaryloxycarbonylation of 2-allylphenol derivatives. Synthesis of chiral lactones via cyclocarbonylation》 was published in Molecular Catalysis in 2020. These research results belong to Abu Seni, Anas; Kollar, Laszlo; Pongracz, Peter. HPLC of Formula: 210169-54-3 The article mentions the following:

Homogeneous catalytic hydroaryloxycarbonylation of 2-allylphenol derivatives I (R1 = H, CH3, OCH3, CHO; R2 = H, COCH3) was performed using palladium complexes toward the corresponding lactones II, III, IV. Reactions were conducted under carbon monoxide atm. in the absence of hydrogen gas. Palladium catalyst was generated in situ, using various phosphine ligands e.g., (4S,5S)-4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane and precursors as Pd(OAc)2, PdCl2, PdCl2(PhCN)2, etc. in the presence of acid additives as HCl, HCOOH, TsOH, etc. In general, chiral 6- III and achiral 7-membered lactones IV were formed dominantly, only trace amounts of the 5-membered lactone II can be identified. Moderate or good enantioselectivity can be achieved using chiral ligands regarding the 6-membered chromanone derivatives III. The regioselectivity of the reaction is particularly effected by catalyst composition and acid co-catalysts and found to be insensitive for substrate substitution. The results came from multiple reactions, including the reaction of (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) 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 aldehydesHPLC of Formula: 210169-54-3

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

《Novel N,N,P-Tridentate Ligands for the Highly Enantioselective Copper-Catalyzed 1,4-Addition of Dialkylzincs to Enones》 was written by Kawamura, Kenjiro; Fukuzawa, Hitomi; Hayashi, Masahiko. Safety of (S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine And the article was included in Organic Letters on August 21 ,2008. The article conveys some information:

Use of 0.25 mol % of the N,N,P-tridentate ligands (S)-QuCH:NCHRCH2PPh2 (Qu = 2-quinolyl) and 0.1 mol % of Cu(OTf)2 enabled the enantioselective 1,4-addition of dialkylzincs to cyclic enones to produce 1,4-adducts in up to 99% ee.(S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine(cas: 286454-86-2Safety of (S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine) was used in this study.

(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.Safety of (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

《Domino Asymmetric Conjugate Addition-Conjugate Addition》 was written by Germain, Nicolas; Schlaefli, Doriane; Chellat, Mathieu; Rosset, Stephane; Alexakis, Alexandre. Application In Synthesis of (1S)-1-(Dicyclohexylphosphino)-2-[(R)-[2-(dicyclohexylphosphino)phenyl](dimethylamino)methyl]ferrocene And the article was included in Organic Letters on April 4 ,2014. The article conveys some information:

In the presence of copper catalysts and nonracemic phosphoramidite, imidazolium, or aminoferrocenylphosphine ligands, ethylmagnesium bromide, trimethylaluminum, and dimethyl- and diethylzinc underwent enantioselective and diastereoselective conjugate addition reactions to cyclopentenones, cyclohexenones, and cycloheptenones followed by trapping with either nitroalkenes or 1,1-bis(phenylsulfonyl)ethylene to give oxoalkyl cycloalkanones in 63-85% yields, 57:43-97:3 dr, and in 86->99.5% ee; the oxoalkyl cycloalkanones were converted by various methods to indenones, a hydrazulenone, a tetrahydrobenzofuran and a tetrahydroindole, and an octahydronaphthalene. In the experiment, the researchers used many compounds, for example, (1S)-1-(Dicyclohexylphosphino)-2-[(R)-[2-(dicyclohexylphosphino)phenyl](dimethylamino)methyl]ferrocene(cas: 1156547-61-3Application In Synthesis of (1S)-1-(Dicyclohexylphosphino)-2-[(R)-[2-(dicyclohexylphosphino)phenyl](dimethylamino)methyl]ferrocene)

(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. 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 (1S)-1-(Dicyclohexylphosphino)-2-[(R)-[2-(dicyclohexylphosphino)phenyl](dimethylamino)methyl]ferrocene

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Mifleur, Alexis; Suisse, Isabelle; Mortreux, Andre; Sauthier, Mathieu published their research in Catalysis Letters in 2021. The article was titled 《Enantioselective Nickel Catalyzed Butadiene Hydroalkoxylation with Ethanol: from Experimental Results to Kinetics Parameters》.Recommanded Product: 210169-54-3 The article contains the following contents:

The enantioselective hydroalkoxylation of butadiene with ethanol has been performed in the presence of nickel-based catalysts and chiral diphosphine ligands. Ee’s up to 77% could be obtained from the use of atropoisomeric chiral ligands such as Segphos. The kinetics parameters of the reaction were determined using a qual. kinetic model to better explain the l/b isomerization and racemization processes observed for long reaction times. 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: 210169-54-3Recommanded Product: 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.Recommanded Product: 210169-54-3

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

《Asymmetric Hydrogenation of 2-Aryl-3-phthalimidopyridinium Salts: Synthesis of Piperidine Derivatives with Two Contiguous Stereocenters》 was published in Organic Letters in 2020. These research results belong to Zheng, Long-Sheng; Wang, Fangyuan; Ye, Xiang-Yu; Chen, Gen-Qiang; Zhang, Xumu. Quality Control of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole The article mentions the following:

Asym. hydrogenation of 2-aryl-3-phthalimidopyridinium salts catalyzed by the Ir/SegPhos catalytic system was described, leading to the corresponding chiral piperidine derivatives bearing two contiguous chiral centers, with high levels of enantioselectivities and diastereoselectivities. A gram-scale experiment has demonstrated the utility of this approach. The phthaloyl group could be easily removed and then smoothly converted to key intermediate (+)-CP-99994 as one of the neurokinin 1 receptor antagonists.(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) 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.Quality Control of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Quality Control of (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine]On May 7, 2021 ,《Copper-Catalyzed Asymmetric Reductions of Aryl/Heteroaryl Ketones under Mild Aqueous Micellar Conditions》 appeared in Organic Letters. The author of the article were Fialho, David M.; Etemadi-Davan, Elham; Langner, Olivia C.; Takale, Balaram S.; Gadakh, Amol; Sambasivam, Ganesh; Lipshutz, Bruce H.. The article conveys some information:

Enantioselective syntheses of nonracemic secondary alcs. have been achieved in an aqueous micellar medium via copper-catalyzed (Cu(OAc)2.H2O/(R)-3,4,5-MeO-MeO-BIPHEP) reduction of aryl/heteroaryl ketones. This methodol. serves as a green protocol to access enantio-enriched alcs. under mild conditions (0-22°C) using a base metal catalyst, together with an inexpensive, innocuous, and convenient stoichiometric hydride source (PMHS). The secondary alc. products are formed in good to excellent yields with ee values greater than 90%. In the experiment, the researchers used (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine](cas: 256390-47-3Quality Control 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. Quality Control of (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine]

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Xiao, Xiong; Yu, Zhi-Xiang published their research in Chemistry – A European Journal in 2021. The article was titled 《Co-Catalyzed Asymmetric Intramolecular [3+2] Cycloaddition of Yne-Alkylidenecyclopropanes and its Reaction Mechanism》.Application In Synthesis of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole The article contains the following contents:

Developing new transition metal-catalyzed asym. cycloadditions for the synthesis of five-membered carbocycles (FMCs) is a research frontier in reaction development due to the ubiquitous presence of chiral FMCs in various functional mols. Reported here is our discovery of a highly enantioselective intramol. [3+2] cycloaddition of yne-alkylidenecyclopropanes (yne-ACPs) to bicyclo[3.3.0]octadiene, e.g., I, and bicyclo[4.3.0]nonadiene mols. using a cheap Co catalyst and com. available chiral ligand (S)-Xyl-BINAP. This reaction avoids the use of precious Pd and Rh catalysts, which are usually the choices for [3+2] reactions with ACPs. The enantiomeric excess in the present reaction can be up to 92%. Cationic cobalt(I) species was suggested by experiments as the catalytic species. DFT calculations showed that this [3+2] reaction starts with oxidative cyclometallation of alkyne and ACP, followed by ring opening of the cyclopropyl (CP) group and reductive elimination to form the cycloadduct. This mechanism is different from previous [3+2] reactions of ACPs, which usually start from CP cleavage, not from oxidative cyclization. The results came from multiple reactions, including the reaction 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) 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

Guo, Rongwei; Lu, Shuiming; Chen, Xuanhua; Tsang, Chi-Wing; Jia, Wenli; Sui-Seng, Christine; Amoroso, Dino; Abdur-Rashid, Kamaluddin published an article on February 5 ,2010. The article was titled 《Synthesis of Chiral Aminophosphines from Chiral Aminoalcohols via Cyclic Sulfamidates》, and you may find the article in Journal of Organic Chemistry.Synthetic Route of C18H24NP The information in the text is summarized as follows:

Protic aminophosphines with multiple chiral centers were synthesized in good yields and high purity by the nucleophilic ring-opening of N-protected cyclic sulfamidates with metal phosphides, followed by hydrolysis and deprotection. This synthetic approach is clean, scalable, and high yielding. The method provides an efficient alternative route for the synthesis of chiral aminophosphines. In the experiment, the researchers used (S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine(cas: 286454-86-2Synthetic Route of C18H24NP)

(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.Synthetic Route of C18H24NP 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

Application of 256390-47-3On May 20, 2016 ,《Direct Catalytic Asymmetric Mannich-Type Reaction of Alkylamides》 appeared in Organic Letters. The author of the article were Arteaga, Fernando Arteaga; Liu, Zijian; Brewitz, Lennart; Chen, Jianyang; Sun, Bo; Kumagai, Naoya; Shibasaki, Masakatsu. The article conveys some information:

Direct enolate formation coupled with subsequent enantioselective C-C bond formation remains a topic of intense interest in asym. catalysis. This methodol. is achieved even with low acidic amides without an electron-withdrawing group at the α-position in the context of a Mannich-type reaction. Acetate-, propionate-, and butyrate-type 7-azaindoline amides served as enolate precursors to afford the desired Mannich adducts with high stereoselectivity, e.g., anti-adducts I (R1 = Ph, 4-MeC6H4, 3-furyl, etc.), and ligand-enabled diastereo-divergency provided access to both anti/syn diastereomers. The facile transformation of the amide moiety ensures the synthetic utility of the Mannich adducts. 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: 256390-47-3Application of 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. 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 of 256390-47-3

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Safety of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxoleIn 2016 ,《Kinetic Resolution of Racemic Allylic Alcohols by Catalytic Asymmetric Substitution of the OH Group with Monosubstituted Hydrazines》 appeared in Chemistry – A European Journal. The author of the article were Yan, Liang; Xu, Jing-Kun; Huang, Chao-Fan; He, Zeng-Yang; Xu, Ya-Nan; Tian, Shi-Kai. The article conveys some information:

A new strategy has been established for the kinetic resolution of racemic allylic alcs. through a palladium/sulfonyl-hydrazide-catalyzed asym. OH-substitution under mild conditions. In the presence of 1 mol % [Pd(allyl)Cl]2, 4 mol % (S)-SegPhos, and 10 mol % 2,5-dichlorobenzenesulfonyl hydrazide, a range of racemic allylic alcs. were smoothly resolved with selectivity factors of more than 400 through an asym. allylic alkylation of monosubstituted hydrazines under air at room temperature Importantly, this kinetic resolution process provided various allylic alcs. and allylic hydrazine derivatives with high enantiopurity. 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