Day: February 22, 2023

Chiral-Squaramide-Catalyzed Sulfa-Michael/Aldol Cascade Reactions for Asymmetric Synthesis of Spirothiochromanones was written by Zhao, Bo-Liang;Du, Da-Ming. And the article was included in Asian Journal of Organic Chemistry in 2015.Synthetic Route of C32H28F6N4O3 This article mentions the following:

In the presence of a quinidine-derived squaramide, arylmethyleneindanones I [R = Ph, 4-FC₆H₄, 2-ClC₆H₄, 4-ClC₆H₄, 4-BrC₆H₄, 2,4-Cl₂C₆H₃, 2-MeC₆H₄, 4-MeC₆H₄, 2-MeOC₆H₄, 4-MeOC₆H₄, 3,4-(MeO)₂C₆H₃, 3-O₂NC₆H₄, 4-O₂NC₆H₄, 1-naphthyl, 2-thienyl; R¹ = H, Br, Cl; R² = H, Me] underwent diastereoselective and enantioselective sulfa-Michael/aldol cascade reactions with 2-mercaptobenzaldehyde to yield spiroindanethiochromandiones II [R = Ph, 4-FC₆H₄, 2-ClC₆H₄, 4-ClC₆H₄, 4-BrC₆H₄, 2,4-Cl₂C₆H₃, 2-MeC₆H₄, 4-MeC₆H₄, 2-MeOC₆H₄, 4-MeOC₆H₄, 3,4-(MeO)₂C₆H₃, 3-O₂NC₆H₄, 4-O₂NC₆H₄, 1-naphthyl, 2-thienyl; R¹ = H, Br, Cl; R² = H, Me]. Under analogous conditions, dialkylidenecycloalkanones III (R³ = Ph, 4-BrC₆H₄, 4-MeC₆H₄; X = CH₂, O; Y = bond, CH₂) underwent diastereoselective and enantioselective sulfa-Michael/aldol cascade reactions to yield spirothiochromanones IV (R³ = Ph, 4-BrC₆H₄, 4-MeC₆H₄; X = CH₂, O; Y = bond, CH₂). This organocatalytic cascade reaction provides easy access to highly functionalized spirothiochromanones with three contiguous stereocenters, including one quaternary center, in excellent yields up to 99% with excellent diastereoselectivity up to >99:1. In the experiment, the researchers used many compounds, for example, 3-((3,5-Bis(trifluoromethyl)phenyl)amino)-4-(((1R)-(6-methoxyquinolin-4-yl)(5-vinylquinuclidin-2-yl)methyl)amino)cyclobut-3-ene-1,2-dione (cas: 1256245-79-0Synthetic Route of C32H28F6N4O3).

3-((3,5-Bis(trifluoromethyl)phenyl)amino)-4-(((1R)-(6-methoxyquinolin-4-yl)(5-vinylquinuclidin-2-yl)methyl)amino)cyclobut-3-ene-1,2-dione (cas: 1256245-79-0) belongs to quinuclidine derivatives. Quinuclidine derivatives are also widely utilized as homogeneous or heterogeneous catalysts in various asymmetric processes such as Morita鈥揃aylis鈥揌illman reactions, Sharpless dihydroxylation reactions, and phase-transfer catalytic reactions. The configuration at C-8 (quinuclidine attachment) and C-9 position (bearing hydroxy group) are important as they help in the orientation of hydroxy group and nitrogen atom of quinuclidine.Synthetic Route of C32H28F6N4O3

Referemce:
Quinuclidine – Wikipedia,
Quinuclidine | C7H13N | ChemSpider

Total Synthesis of Tryprostatin B: Synthesis and Asymmetric Phase-Transfer-Catalyzed Reaction of Prenylated Gramine Salt was written by Huisman, Matthew;Rahaman, Mizzanoor;Asad, Sharif;Oehm, Sarah;Novin, Sherwin;Rheingold, Arnold L.;Hossain, M. Mahmun. And the article was included in Organic Letters in 2019.SDS of cas: 200132-54-3 This article mentions the following:

A concise and efficient total synthesis of microtubule inhibitor tryprostatin B is described. The key step is the preparation of a diprenylated gramine salt. In this step, the prenyl group is incorporated at the 2-position of the indole moiety by direct lithiation of the Boc-protected gramine. We also developed and optimized the asym. phase-transfer-catalyzed reaction with the diprenylated gramine salt to provide the C2-prenyl tryptophan intermediate resulting in 93% enantiomeric excess (ee) and 65% yield. The total synthesis of tryprostatin B is done in six steps with 35% overall yield. In the experiment, the researchers used many compounds, for example, (1S,2S,4S,5R)-2-((R)-(Allyloxy)(quinolin-4-yl)methyl)-1-(anthracen-9-ylmethyl)-5-vinylquinuclidin-1-ium bromide (cas: 200132-54-3SDS of cas: 200132-54-3).

(1S,2S,4S,5R)-2-((R)-(Allyloxy)(quinolin-4-yl)methyl)-1-(anthracen-9-ylmethyl)-5-vinylquinuclidin-1-ium bromide (cas: 200132-54-3) belongs to quinuclidine derivatives. The development of synthetic approaches for efficient construction of novel quinuclidine derivatives is of great significance. Quinuclidine derivatives can also be formed conveniently by introducing substituents into the quinuclidine ring, but the scope of this method is rather limited by the available source of starting materials.SDS of cas: 200132-54-3

Referemce:
Quinuclidine – Wikipedia,
Quinuclidine | C7H13N | ChemSpider

Design and synthesis of chiral hyperbranched polymers containing cinchona squaramide moieties and their catalytic activity in the asymmetric Michael addition reaction was written by Chhanda, Sadia Afrin;Itsuno, Shinichi. And the article was included in Journal of Catalysis in 2019.Electric Literature of C42H44N6O2 This article mentions the following:

Chiral hyperbranched polymers (HBP) containing cinchona alkaloids were synthesized using a Mizoroki-Heck (MH) coupling polymerization reaction between a cinchona squaramide dimer and tri- or tetra-substituted aromatic iodides. This was a new type of polymeric chiral organocatalyst. We found that the as-obtained chiral HBPs show excellent catalytic activity in the asym. Michael reaction. Almost perfect enantioselectivity (>99% ee) was achieved in the reaction of 尾-ketoester and trans-尾-nitrostyrene. The three-dimensional network structure of the chiral HBPs is structurally robust and can be reused for further reaction without any loss in their catalytic activity. In the experiment, the researchers used many compounds, for example, 3,4-Bis(((1S)-quinolin-4-yl((2S)-5-vinylquinuclidin-2-yl)methyl)amino)cyclobut-3-ene-1,2-dione (cas: 1204591-50-3Electric Literature of C42H44N6O2).

3,4-Bis(((1S)-quinolin-4-yl((2S)-5-vinylquinuclidin-2-yl)methyl)amino)cyclobut-3-ene-1,2-dione (cas: 1204591-50-3) belongs to quinuclidine derivatives.The reactions of quinuclidine compounds that lead to opening of the 1-azabi-cyclic system at the N-C and C-C bonds to give piperidine derivatives or, via subsequent rearrangements, derivatives of other heterocyclic systems, are correlated. Processes involving the fragmentation of quinuclidines in chemical reactions and under electron impact and reactions involving expansion of the quinuclidine ring and intermediate cleavage of the bicyclic system are examined.聽 Asymmetric construction of quinuclidine derivatives has been realized by an iridium-catalyzed allylic dearomatization reaction. The catalytic system, derived from [Ir(cod)Cl]2 and the Feringa ligand, tolerates a broad range of substrates. A large array of quinuclidine derivatives can be obtained under mild conditions in good to excellent yields (68%鈥?6%), diastereoselectivity (up to >20/1 dr), and enantioselectivity (up to >99% ee).Electric Literature of C42H44N6O2

Referemce:
Quinuclidine – Wikipedia,
Quinuclidine | C7H13N | ChemSpider

Cation-Directed Enantioselective N-Functionalization of Pyrroles was written by Armstrong, Roly J.;D’Ascenzio, Melissa;Smith, Martin D.. And the article was included in Synlett in 2016.Reference of 69221-14-3 This article mentions the following:

A catalytic enantioselective N-functionalization of pyrroles has been developed. Imines formed in situ via condensation underwent cation-directed cyclization with complete N-regioselectivity. The cyclized products were obtained with enantiomeric ratios up to 96:4 for aldimine substrates and up to 99:1 for trifluoromethyl ketimines. The reaction proceeds without an acidifying group on the pyrrole and offers a new approach to the generation of chiral nonracemic aminals. In the experiment, the researchers used many compounds, for example, (1S,2R,4S,5R)-1-Benzyl-2-(hydroxy(quinolin-4-yl)methyl)-5-vinylquinuclidin-1-ium chloride (cas: 69221-14-3Reference of 69221-14-3).

(1S,2R,4S,5R)-1-Benzyl-2-(hydroxy(quinolin-4-yl)methyl)-5-vinylquinuclidin-1-ium chloride (cas: 69221-14-3) belongs to quinuclidine derivatives. Quinuclidine acts as a catalyst, a chemical building block and is used in organic synthesis. As a ligand, quinuclidine is useful in the studies of OsO4-catalyzed dihydroxylation of olefins. It plays an important role in the formation of onium salts used testing of PAC-antagonist activity.Reference of 69221-14-3

Referemce:
Quinuclidine – Wikipedia,
Quinuclidine | C7H13N | ChemSpider

Free radical-mediated aryl amination: a practical synthesis of (R)- and (S)-7-azaindoline 伪-amino acid was written by Srinivasan, Jayasree M.;Burks, Heather E.;Smith, Colin R.;Viswanathan, Rajesh;Johnston, Jeffrey N.. And the article was included in Synthesis in 2005.Electric Literature of C37H37BrN2O This article mentions the following:

Two nonnatural proline derivatives, (S)- and (R)-7-azaindoline 伪-amino acids I, have been prepared and isolated as their trifluoroacetate salts on gram scale. The convergent sequence (6 steps from 2-bromopyridine) employs phase transfer-catalyzed asym. alkylation of Ph₂C:NCH₂CO₂Bu-t with 3-bromomethyl-2-bromopyridine to give (S)- and (R)-2-[N-(diphenylmethylene)amino]-3-(2-bromo-3-pyridyl)propanoates II, followed by their free radical-mediated aryl amination leading to cyclization. Implementation of the solid-liquid phase transfer conditions requires manual pulverization of CsOH, efficient mech. stirring, and effective low temperature control. This large scale free radical cyclization protocol replaces benzene solvent with toluene without complication, and the crystalline nature of the intermediates and final product enables straightforward purification at each stage, including enantiomeric enrichment. In the experiment, the researchers used many compounds, for example, (1S,2S,4S,5R)-2-((R)-(Allyloxy)(quinolin-4-yl)methyl)-1-(anthracen-9-ylmethyl)-5-vinylquinuclidin-1-ium bromide (cas: 200132-54-3Electric Literature of C37H37BrN2O).

(1S,2S,4S,5R)-2-((R)-(Allyloxy)(quinolin-4-yl)methyl)-1-(anthracen-9-ylmethyl)-5-vinylquinuclidin-1-ium bromide (cas: 200132-54-3) belongs to quinuclidine derivatives. Quinuclidine acts as a catalyst, a chemical building block and is used in organic synthesis. It is employed to prepare quinine and alkaloids. Carbamoyl boranes are generally prepared as adducts with tertiary amines, such as trialkyl amines, pyridine, or quinuclidine, via two synthetic approaches based either on amidation of amine-carboxyborane adducts or on hydrolysis of amine-cyanoboranes.Electric Literature of C37H37BrN2O

Referemce:
Quinuclidine – Wikipedia,
Quinuclidine | C7H13N | ChemSpider

Modular and Tunable Chemosensor Scaffold for Divalent Zinc was written by Shults, Melissa D.;Pearce, Dierdre A.;Imperiali, Barbara. And the article was included in Journal of the American Chemical Society in 2003.Application of 200132-54-3 This article mentions the following:

A modular peptide scaffold was developed for fluorescent sensing of divalent zinc. The signaling component of the chemosensor is the chelation-sensitive fluorophore 8-hydroxy-5-(N,N-dimethylsulfonamido)-2-methylquinoline, which is prepared as the protected amino acid derivative Fmoc-Sox-OH and integrated into peptide sequences. Nineteen synthetic peptides incorporating the signaling element exhibit a range of affinities for Zn²⁺ through variation and number of Zn²⁺ ligands, ligand arrangement and the 尾-turn sequence that acts as a preorganization element between the ligands. The stoichiometry of the peptide-Zn²⁺ complexes is evaluated by several criteria. The fluorescence response of these peptides to pH and various important metal ions is reported. Eleven of these sequences form only 1:1 complexes with Zn²⁺ and their affinities range from 10 nM to nearly 1 渭M. When used in concert, these sensors can provide Zn²⁺ concentration information in a valuable range. In the experiment, the researchers used many compounds, for example, (1S,2S,4S,5R)-2-((R)-(Allyloxy)(quinolin-4-yl)methyl)-1-(anthracen-9-ylmethyl)-5-vinylquinuclidin-1-ium bromide (cas: 200132-54-3Application of 200132-54-3).

(1S,2S,4S,5R)-2-((R)-(Allyloxy)(quinolin-4-yl)methyl)-1-(anthracen-9-ylmethyl)-5-vinylquinuclidin-1-ium bromide (cas: 200132-54-3) belongs to quinuclidine derivatives. Quinuclidine is found as a structural component of some biomolecules including quinine. The configuration at C-8 (quinuclidine attachment) and C-9 position (bearing hydroxy group) are important as they help in the orientation of hydroxy group and nitrogen atom of quinuclidine.Application of 200132-54-3

Referemce:
Quinuclidine – Wikipedia,
Quinuclidine | C7H13N | ChemSpider

A systematic study on the use of different organocatalytic activation modes for asymmetric conjugated addition reactions of isoindolinones was written by Scorzelli, Francesco;Di Mola, Antonia;De Piano, Francesco;Tedesco, Consiglia;Palombi, Laura;Filosa, Rosanna;Waser, Mario;Massa, Antonio. And the article was included in Tetrahedron in 2017.Formula: C26H29ClN2O This article mentions the following:

The authors describe a series of new asym. Michael reactions of 3-carboxylate-substituted isoindolinones used as nucleophiles in the synthesis of valuable chiral tetrasubstituted derivatives It has been shown that the reactivity and enantioselectivity strongly depend on the substitution pattern of the isoindolinone, requiring either cinchona-alkaloid based phase transfer catalysts or bifunctional tertiary amines organocatalysts. Moreover, prolinol-TMS ether-based secondary amine catalysts permitted the development of Michael/cyclization tandem reaction with cinnamaldehyde for the synthesis of aza-polycyclic derivatives In the experiment, the researchers used many compounds, for example, (1S,2R,4S,5R)-1-Benzyl-2-(hydroxy(quinolin-4-yl)methyl)-5-vinylquinuclidin-1-ium chloride (cas: 69221-14-3Formula: C26H29ClN2O).

(1S,2R,4S,5R)-1-Benzyl-2-(hydroxy(quinolin-4-yl)methyl)-5-vinylquinuclidin-1-ium chloride (cas: 69221-14-3) belongs to quinuclidine derivatives. Quinuclidine acts as a catalyst, a chemical building block and is used in organic synthesis. It is employed to prepare quinine and alkaloids. Quinuclidine derivatives can also be formed conveniently by introducing substituents into the quinuclidine ring, but the scope of this method is rather limited by the available source of starting materials.Formula: C26H29ClN2O

Referemce:
Quinuclidine – Wikipedia,
Quinuclidine | C7H13N | ChemSpider

Optimization of a ligand immobilization and azide group endcapping concept via “Click-Chemistry” for the preparation of adsorbents for antibody purification was written by Horak, Jeannie;Hofer, Stefan;Lindner, Wolfgang. And the article was included in Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences in 2010.Product Details of 6530-09-2 This article mentions the following:

This report describes and compares different strategies to deactivate (endcap) epoxide groups and azide groups on bio-chromatog. support surfaces, before and after ligand attachment. Adsorbents possessing epoxide groups were deactivated using acidic hydrolysis or were endcapped with 2-mercaptoethanol or 2-ethanolamine. The influence of surface-bound 2-ethanolamine was demonstrated for the triazine-type affinity adsorbent B14-2LP-FractoAIMs-1, which was tested in combination with the weak anion exchange material 3-aminoquinuclidine-FractoAIMs-3 (AQ-FA3). Azide groups were modified with 2-propargyl alc. using Click-Chem. Besides the conventional one-pot Click reaction, an alternative approach was introduced. This optimized Click protocol was employed (i) for the preparation of the weak anion exchange material AdQ-triazole-Fractogel (AdQ-TRZ-FG) and (ii) for the endcapping of residual azide groups with 3-propargyl alc. Using the new Click reaction protocol the ligand immobilization rate was doubled from 250 to 500 渭mol/g dry adsorbent. Furthermore, the modified support surface was proven to be inert towards the binding of IgG as well as feed impurities. A thorough evaluation of modified surfaces and adsorbents was performed with dynamic binding experiments using cell culture supernatant containing monoclonal human IgG (h-IgG-1). Besides SDS-Page, a recently introduced Protein A-size exclusion HPLC method (PSEC-HPLC) was used to visualize the feed impurity composition and the IgG content of all collected sample fractions in simple PSEC-Plots. A surprising outcome of this study was the irreversible binding of IgG to azide modified surfaces. It was found that organic azide compounds, e.g. 1-azide-3-(2-propen-1-yloxy)-2-propanol (AGE-N3) promote antibody aggregation to a slightly higher extent than the inorganic sodium azide. The possibility that the Hofmeister Series of salt anions may be applicable to predict the properties of the corresponding organic compounds is discussed. In the experiment, the researchers used many compounds, for example, 3-Aminoquinuclidine dihydrochloride (cas: 6530-09-2Product Details of 6530-09-2).

3-Aminoquinuclidine dihydrochloride (cas: 6530-09-2) belongs to quinuclidine derivatives. Quinuclidine exists in a number of naturally occurring compounds, biologically active agents, and privileged catalysts and ligands for asymmetric catalysis. The reactions of quinuclidine compounds that lead to opening of the 1-azabi-cyclic system at the N-C and C-C bonds to give piperidine derivatives or, via subsequent rearrangements, derivatives of other heterocyclic systems, are correlated.Product Details of 6530-09-2

Referemce:
Quinuclidine – Wikipedia,
Quinuclidine | C7H13N | ChemSpider

Ag-Catalyzed Asymmetric Interrupted Barton-Zard Reaction Enabling the Enantioselective Dearomatization of 2- and 3-Nitroindoles was written by Yuan, Wei-Cheng;Chen, Xin-Meng;Zhao, Jian-Qiang;Zhang, Yan-Ping;Wang, Zhen-Hua;You, Yong. And the article was included in Organic Letters in 2022.Synthetic Route of C39H38N3O2P This article mentions the following:

Authors disclose a Ag-catalyzed asym. interrupted Barton-Zard reaction of 伪-aryl substituted isocyanoacetates with 2- and 3-nitroindoles, which enables the dearomatization of nitroindoles and hence offers rapid access to an array of optically active tetrahydropyrrolo[3,4-b]indole derivatives bearing three contiguous stereogenic centers including two tetrasubstituted chiral carbon atoms with pretty outcomes (up to 99% yield, 91:9 dr and 96% ee). The synthetic potential of the protocol was showcased by the gram-scale reaction and versatile transformations of product. In the experiment, the researchers used many compounds, for example, 2-(Diphenylphosphino)-N-((S)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)benzamide (cas: 1630973-03-3Synthetic Route of C39H38N3O2P).

2-(Diphenylphosphino)-N-((S)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)benzamide (cas: 1630973-03-3) belongs to quinuclidine derivatives.The reactions of quinuclidine compounds that lead to opening of the 1-azabi-cyclic system at the N-C and C-C bonds to give piperidine derivatives or, via subsequent rearrangements, derivatives of other heterocyclic systems, are correlated. Processes involving the fragmentation of quinuclidines in chemical reactions and under electron impact and reactions involving expansion of the quinuclidine ring and intermediate cleavage of the bicyclic system are examined.聽 The reactions of quinuclidine compounds that lead to opening of the 1-azabi-cyclic system at the N-C and C-C bonds to give piperidine derivatives or, via subsequent rearrangements, derivatives of other heterocyclic systems, are correlated.Synthetic Route of C39H38N3O2P

Referemce:
Quinuclidine – Wikipedia,
Quinuclidine | C7H13N | ChemSpider

Synthesis of Fmoc-protected (S)-3,5-dibromophenylalanine in presence of a phase transfer catalyst or a chiral catalyst was written by Wang, Qinting;Zhao, Shuai;Jin, Lei;Chen, Xin. And the article was included in Youji Huaxue in 2016.Name: (1S,2S,4S,5R)-2-((R)-(Allyloxy)(quinolin-4-yl)methyl)-1-(anthracen-9-ylmethyl)-5-vinylquinuclidin-1-ium bromide This article mentions the following:

Two methods of catalytic asym. synthesis of (S)-3,5-dibromophenylalanine were presented. One approach was to use asym. alkylation reaction starting from diphenylimine glycine tert-Bu ester and 3,5-dibromobenzyl bromide, with O-allyl-N-9-anthracene Me bromide cinchonidine as phase-transfer catalyst, and the (S)-3,5-dibromophenylalanine derivative was obtained (up to 94.9% ee). The optimized conditions of asym. phase transfer catalytic alkylation were explored. Another method was to employ asym. hydrogenation starting from 2-acetylamino-3-(3,5-dibromophenyl) acrylic acid with bis(1,5-cyclooctadiene)rhodium trifluoromethanesulfonate and (R)-diphenylphosphino-N-methyl-1-[(S)-2-diphenyl-phosphinoferrocenyl]ethylamine [(R)-Me BoPhoz] as chiral catalyst. (S)-3,5-Dibromophenylalanine hydrochloride was obtained after hydrolysis. By Fmoc protection, Fmoc-(S)-3,5-dibromophenylalanine was obtained (up to 94.7% ee). By comparison of the two methods, the first one gives higher overall yield and a little bit better selectivity, and is more suitable for the synthesis of other chiral dihalo-substituent phenylalanine derivatives In the experiment, the researchers used many compounds, for example, (1S,2S,4S,5R)-2-((R)-(Allyloxy)(quinolin-4-yl)methyl)-1-(anthracen-9-ylmethyl)-5-vinylquinuclidin-1-ium bromide (cas: 200132-54-3Name: (1S,2S,4S,5R)-2-((R)-(Allyloxy)(quinolin-4-yl)methyl)-1-(anthracen-9-ylmethyl)-5-vinylquinuclidin-1-ium bromide).

(1S,2S,4S,5R)-2-((R)-(Allyloxy)(quinolin-4-yl)methyl)-1-(anthracen-9-ylmethyl)-5-vinylquinuclidin-1-ium bromide (cas: 200132-54-3) belongs to quinuclidine derivatives. Quinuclidine exists in a number of naturally occurring compounds, biologically active agents, and privileged catalysts and ligands for asymmetric catalysis. Quinuclidine derivatives can also be formed conveniently by introducing substituents into the quinuclidine ring, but the scope of this method is rather limited by the available source of starting materials.Name: (1S,2S,4S,5R)-2-((R)-(Allyloxy)(quinolin-4-yl)methyl)-1-(anthracen-9-ylmethyl)-5-vinylquinuclidin-1-ium bromide

Referemce:
Quinuclidine – Wikipedia,
Quinuclidine | C7H13N | ChemSpider