Day: October 17, 2022

The author of 《Tunable Bifunctional Phosphine-Squaramide Promoted Morita-Baylis-Hillman Reaction of N-Alkyl Isatins with Acrylates》 were Dong, Ze; Yan, Chao; Gao, Yongzhi; Dong, Chune; Qiu, Guofu; Zhou, Hai-Bing. And the article was published in Advanced Synthesis & Catalysis in 2015. Recommanded Product: (S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine The author mentioned the following in the article:

A series of highly tunable bifunctional phosphine-squaramide H-bond donor organocatalysts I (R1 = i-Pr, Ph, t-Bu; R2 = 4-FC6H4, 3,5-(CF3)2C6H3, 3,5-(CF3)2C6H3CH2) has been synthesized from inexpensive and com. available β-amino alcs. in moderate yields. Catalyst I (R1 = t-Bu; R2 = 3,5-(CF3)2C6H3) can efficiently promote the asym. Morita-Baylis-Hillman (MBH) reaction of N-alkyl isatins with acrylate esters providing the chiral 3-substituted 3-hydroxy-2-oxindoles II (R3 = H, 4-Br, 5-F, etc.; R4 = Me, i-Pr, allyl, Bn, etc.; R5 = Me, Et, Bu, t-Bu) in good yields and enantioselectivities (up to 93 % yield and 95 % ee), in which the challenging substrate tert-Bu acrylate tert-Bu prop-2-enoate, provided the best ee value to date. This methodol. was applied successfully in the synthesis of chiral cyclic spiropyrrolizidineoxindole and γ-butyrolactone derivatives without enantioselectivity deterioration. The KIE experiments show that the electrophilic addition of N-Me isatin to the complex of acrylate ester and phophine-squaramide is the rate-determining step of the asym. MBH reaction. After reading the article, we found that the author used (S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine(cas: 286454-86-2Recommanded Product: (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.Recommanded Product: (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

Application of 286454-86-2On March 17, 2017, Su, Hsin Y.; Taylor, Mark S. published an article in Journal of Organic Chemistry. The article was 《P-Stereogenic β-aminophosphines: preparation and applications in enantioselective organocatalysis》. The article mentions the following:

The synthesis of stereodefined β-aminophosphines ArPhPCH2CH(tBu)NH2 (1a,b, Ar = 2-MeOC6H4) having both carbon- and phosphorus-based chirality centers is described. The method involves resolution of a mixture of β-aminophosphine oxide diastereomers accessed by ring-opening of an amino alc.-derived cyclic sulfamidate. A stereospecific, borane-promoted reduction of β-aminophosphine oxides, which occurs under mild conditions and with inversion of configuration at phosphorus, is a key step in this process. The products obtained are new building blocks for the synthesis of P-chiral ligands and organocatalysts. In a proof-of-concept application in organocatalysis, the diastereomeric P-chiral β-aminophosphine-based bifunctional thioureas displayed significantly different activities in the Morita-Baylis-Hillman reaction of Me acrylate with benzaldehyde derivatives In the experiment, the researchers used many compounds, for example, (S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine(cas: 286454-86-2Application of 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.Application of 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

《Mechanistic insights into Cu-catalyzed enantioselective Friedel-Crafts reaction between indoles and 2-aryl-N-sulfonylaziridines》 was written by Wang, Ping; Zhao, Yang; Chapagain, Biplav; Yang, Yonggang; Liu, Wei; Wang, Yong. Product Details of 210169-54-3 And the article was included in Catalysis Science & Technology in 2020. The article conveys some information:

Computational studies were successfully carried out to provide mechanistic insights into LCu-catalyzed (L = (S)-Segphos ligand) Friedel-Crafts (F-C) reaction between indoles and 2-aryl-N-sulfonylaziridines. The proposed enantioselective mechanistic roles for the LCu-catalyzed F-C reaction were carefully considered: C-N bond cleavage through a three-membered ring transition state, C-C bond formation, oxidative addition, and reductive elimination. Through the energy decomposition anal. (EDA) on all possible transition states of the rate-determining step (RDS), the smaller ΔEdef(total) and the larger ΔEint were found in TS3R, resulting in the lowest activation energy (ΔE#). In other words, TS3R was the most kinetically favorable with the lowest activation barrier. Afterwards, the noncovalent interactions (C-H···π and π···π) and the steric effects were identified as playing a pivotal role in a favorable transition state for the C-C bond formation. In addition, the frontier MO (FMO) revealed that the smallest energy gap (5.2836 eV) between the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) was found in TS3R.(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Product Details 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: 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.Product Details of 210169-54-3

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Synthetic Route of C38H28O4P2In 2018 ,《Iridium-catalyzed Asymmetric Hydrogenation of Polycyclic Pyrrolo/Indolo[1,2-a]quinoxalines and Phenanthridines》 appeared in Advanced Synthesis & Catalysis. The author of the article were Hu, Shu-Bo; Zhai, Xiao-Yong; Shen, Hong-Qiang; Zhou, Yong-Gui. The article conveys some information:

Through in-situ protection of hydrogenation products with acetic anhydride to inhibit rearomatization and poisoning effect, an iridium-catalyzed enantioselective hydrogenation of polycyclic nitrogen-containing heteroaromatics – pyrrolo/indolo[1,2-a]quinoxalines and phenanthridines was successfully developed, providing a facile access to chiral dihydropyrrolo/indolo[1,2-a]quinoxalines and dihydrophenanthridines with up to 98% ee. The strategy featured broad substrate scope, easy operation and potential medicinal application.(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) 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 aldehydesSynthetic Route of C38H28O4P2

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

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

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

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