Browse
Submit Data
Databases
API
Help

Dataset Information

12 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Chiral ¹H NMR of Atropisomeric Quinazolinones With Enantiopure Phosphoric Acids.

ABSTRACT: A chiral phosphoric acid promoted enantioselective NMR analysis of atropisomeric quinazolinones was described, in which a variety of racemic arylquinazolinones such as afloqualone and IC-87114 were well recognized with up to 0. 21 ppm ??? value. With this method, the optical purities of different non-racemic substrates can be fast evaluated with high accuracy.

SUBMITTER: Wu C

PROVIDER: S-EPMC6107746 | biostudies-literature | 2018

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Chiral <sup>1</sup>H NMR of Atropisomeric Quinazolinones With Enantiopure Phosphoric Acids.

Wu Chaofei C Liu Hongxin H Li Juan J Xiao Hong-Ping HP Li Xinhua X Jiang Jun J

Frontiers in chemistry 20180817

A chiral phosphoric acid promoted enantioselective NMR analysis of atropisomeric quinazolinones was described, in which a variety of racemic arylquinazolinones such as afloqualone and IC-87114 were well recognized with up to 0. 21 ppm ΔΔδ value. With this method, the optical purities of different non-racemic substrates can be fast evaluated with high accuracy. ...[more]

PMID: 30175093

Similar Datasets

Chiral Phosphoric Acid Promoted Chiral 1H NMR Analysis of Atropisomeric Quinolines.

Project description:An efficient enantioselective NMR analysis of atropisomeric quinolines in the promotion of chiral phosphoric acid is described, in which a variety of racemic 4-aryl quinolines were well-recognized with up to 0.17 ppm ΔΔδ value. Additionally, the optical purities of different nonracemic substrates could be evaluated fast via NMR analysis with high accuracy.

| S-EPMC8222546 | biostudies-literature

Highly enantioselective hydrogenation of enamides catalyzed by chiral phosphoric acids.

Project description:A highly enantioselective hydrogenation of enamides catalyzed by a dual chiral-achiral acid system was developed. By employing a substoichiometric amount of a chiral phosphoric acid and acetic acid, catalyst loadings as low as 1 mol % of the chiral catalyst were sufficient to provide excellent yield and enantioselectivity of the reduction product.

| S-EPMC2765520 | biostudies-literature

Low-Energy Collisions of Protonated Enantiopure Amino Acids with Chiral Target Gases.

Project description:Here we report on the gas-phase interactions between protonated enantiopure amino acids (L- and D-enantiomers of Met, Phe, and Trp) and chiral target gases [(R)- and (S)-2-butanol, and (S)-1-phenylethanol] in 0.1-10.0 eV low-energy collisions. Two major processes are seen to occur over this collision energy regime, collision-induced dissociation and ion-molecule complex formation. Both processes were found to be independent of the stereo-chemical composition of the interacting ions and targets. These data shed light on the currently debated mechanisms of gas-phase chiral selectivity by demonstrating the inapplicability of the three-point model to these interactions, at least under single collision conditions. Graphical Abstract.

| S-EPMC5707228 | biostudies-literature

Asymmetric cross-dehydrogenative coupling enabled by the design and application of chiral triazole-containing phosphoric acids.

Project description:This report describes the development of an enantioselective C-N bond-forming reaction to produce 1,2,3,4-tetrahydroisoquinoline-derived cyclic aminals catalyzed by chiral phosphate anions. Central to the success of this goal was the design of a library of 3,3'-triazolyl BINOL-derived phosphoric acids capable of forming attractive hydrogen-bonding interactions with the peptide-like substrate. We envision this work will offer an alternative to the conventional strategy of increasing catalyst steric bulk to improve enantioselectivity with BINOL-derived phosphoric acids.

| S-EPMC4117382 | biostudies-literature

Internal acidity scale and reactivity evaluation of chiral phosphoric acids with different 3,3'-substituents in Bronsted acid catalysis.

Project description:The concept of hydrogen bonding for enhancing substrate binding and controlling selectivity and reactivity is central in catalysis. However, the properties of these key hydrogen bonds and their catalyst-dependent variations are extremely difficult to determine directly by experiments. Here, for the first time the hydrogen bond properties of a whole series of BINOL-derived chiral phosphoric acid (CPA) catalysts in their substrate complexes with various imines were investigated to derive the influence of different 3,3'-substituents on the acidity and reactivity. NMR 1H and 15N chemical shifts and 1 J NH coupling constants of these hydrogen bonds were used to establish an internal acidity scale corroborated by calculations. Deviations from calculated external acidities reveal the importance of intermolecular interactions for this key feature of CPAs. For CPAs with similarly sized binding pockets, a correlation of reactivity and hydrogen bond strengths of the catalyst was found. A catalyst with a very small binding pocket showed significantly reduced reactivities. Therefore, NMR isomerization kinetics, population and chemical shift analyses of binary and ternary complexes as well as reaction kinetics were performed to address the steps of the transfer hydrogenation influencing the overall reaction rate. The results of CPAs with different 3,3'-substituents show a delicate balance between the isomerization and the ternary complex formation to be rate-determining. For CPAs with an identical acidic motif and similar sterics, reactivity and internal acidity correlated inversely. In cases where higher sterical demand within the binary complex hinders the binding of the second substrate, the correlation between acidity and reactivity breaks down.

| S-EPMC6977555 | biostudies-literature

A Gallium-based Chiral Solvating Agent Enables the Use of <sup>1</sup>H NMR Spectroscopy to Differentiate Chiral Alcohols.

Project description:In situ, direct 1H NMR chiral analysis by using chiral solvating agents is a convenient and efficient analytical technique. Here we developed a Ga-based chiral anionic metal complex for 1H NMR chiral analysis of alcohols. Utilizing the optimal pKa value, the Ga complex was able to differentiate 1H NMR signals of each (R)- and (S)-enantiomer of alcohols, measured at room temperature. This direct 1H NMR chiral analysis of alcohols was used to rapidly determine enantiomeric excess and conversion in a kinetic resolution and an asymmetric synthesis.

| S-EPMC6704394 | biostudies-literature

Catalytic asymmetric oxo-Diels-Alder reactions with chiral atropisomeric biphenyl diols.

Project description:New chiral atropisomeric biphenyl diols 3, 4 and 6 containing additional peripheral chiral centers with different steric bulkiness and/or electronic properties were synthesized. The X-ray crystal structure of 3 shows the formation of a supramolecular structure whereas that of 6, containing additional CF3 substituents, shows the formation of a monomeric structure. Diols 1-6 were found to be active organocatalysts in oxo-Diels-Alder reactions in which 2 recorded a 72% ee with trimethylacetaldehyde as a substrate.

| S-EPMC6541354 | biostudies-literature

Asymmetric Allylation Catalyzed by Chiral Phosphoric Acids: Stereoselective Synthesis of Tertiary Alcohols and a Reagent-Based Switch in Stereopreference.

Project description:The substrate scope of the asymmetric allylation with zinc organyls catalyzed by 3,3-bis(2,4,6-triisopropylphenyl)-1,1-binaphthyl-2,2-diyl hydrogenphosphate (TRIP) has been extended to non-cyclic ester organozinc reagents and ketones. Tertiary chiral alcohols are obtained with ee's up to 94% and two stereogenic centers can be created. Compared to the previous lactone reagent the stereopreference switches almost completely, proving the fact that the nature of the organometallic compound is of immense importance for the asymmetry of the product.

| S-EPMC8359974 | biostudies-literature

Chiral discrimination of ?-hydroxy acids and N-Ts-?-amino acids induced by tetraaza macrocyclic chiral solvating agents by using 1H NMR spectroscopy.

Project description:In the field of chiral recognition, reported chiral discrimination by 1H NMR spectroscopy has mainly focused on various chiral analytes with a single chiral center, regarded as standard chiral substrates to evaluate the chiral discriminating abilities of a chiral auxiliary. Among them, chiral ?-hydroxy acids, ?-amino acids and their derivatives are chiral organic molecules involved in a wide variety of biological processes, and also play an important role in the area of preparation of pharmaceuticals, as they are part of the synthetic process in the production of chiral drug intermediates and protein-based drugs. In this paper, several ?-hydroxy acids and N-Ts-?-amino acids were used to evaluate the chiral discriminating abilities of tetraaza macrocyclic chiral solvating agents (TAMCSAs) 1a-1d by 1H NMR spectroscopy. The results indicate that ?-hydroxy acids and N-Ts-?-amino acids were successfully discriminated in the presence of TAMCSAs 1a-1d by 1H NMR spectroscopy in most cases. The enantiomers of the ?-hydroxy acids and N-Ts-?-amino acids were assigned based on the change of integration of the 1H NMR signals of the corresponding protons. The enantiomeric excesses (ee) of N-Ts-?-amino acids 11 with different optical compositions were calculated based on the integration of the 1H NMR signals of the CH3 protons (Ts group) of the enantiomers of (R)- and (S)-11 in the presence of TAMCSA 1b. At the same time, the possible chiral discriminating behaviors have been discussed by means of the Job plots of (±)-2 with TAMCSAs 1b and proposed theoretical models of the enantiomers of 2 and 6 with TAMCSA 1a, respectively.

| S-EPMC5363180 | biostudies-literature

Phosphoric acid-catalyzed atroposelective construction of axially chiral arylpyrroles.

Project description:Axially chiral arylpyrroles are key components of pharmaceuticals and natural products as well as chiral catalysts and ligands for asymmetric transformations. However, the catalytic enantioselective construction of optically active arylpyrroles remains a formidable challenge. Here we disclose a highly efficient strategy to access enantioenriched axially chiral arylpyrroles by means of organocatalytic atroposelective desymmetrization and kinetic resolution. Depending on the remote control of chiral catalyst, the arylpyrroles were obtained in high yields and excellent enantioselectivities under mild reaction conditions. This strategy tolerates a wide range of functional groups, providing a facile avenue to approach axially chiral arylpyrroles from simple and readily available starting materials. Selected arylpyrrole products proved to be efficient chiral ligands in asymmetric catalysis and also important precursors for further synthetic transformations into highly functionalized pyrroles with potential bioactivity, especially the axially chiral fully substituted arylpyrroles.

| S-EPMC6361918 | biostudies-literature