Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

A Bronsted acid catalyst for the enantioselective protonation reaction.

ABSTRACT: A highly reactive and robust chiral Brønsted acid catalyst, chiral N-triflyl thiophosphoramide, was developed. The first metal-free Brønsted acid catalyzed enantioselective protonation reaction of silyl enol ethers was demonstrated using this chiral Brønsted acid catalyst. The catalyst loading could be reduced to 0.05 mol % without any deleterious effect on the enantioselectivity.

SUBMITTER: Cheon CH

PROVIDER: S-EPMC2559973 | biostudies-literature | 2008 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

A Brønsted acid catalyst for the enantioselective protonation reaction.

Cheon Cheol Hong CH Yamamoto Hisashi H

Journal of the American Chemical Society 20080627 29

A highly reactive and robust chiral Brønsted acid catalyst, chiral N-triflyl thiophosphoramide, was developed. The first metal-free Brønsted acid catalyzed enantioselective protonation reaction of silyl enol ethers was demonstrated using this chiral Brønsted acid catalyst. The catalyst loading could be reduced to 0.05 mol % without any deleterious effect on the enantioselectivity. ...[more]

PMID: 18582053

Similar Datasets

Silica gel-immobilised chiral 1,2-benzenedisulfonimide: a Bronsted acid heterogeneous catalyst for enantioselective multicomponent Passerini reaction.

Project description:A chiral heterogeneous catalyst derivative of (-)-4,5-dimethyl-3,6-bis(1-naphthyl)-1,2-benzenedisulfonimide is proven here to be efficient in a three-component asymmetric Passerini protocol, carried out in a deep eutectic solvent. Reaction conditions are mild and green, while enantioselectivity is excellent. The catalyst was easily recovered and reused with no decrease in its catalytic activity.

| S-EPMC9037113 | biostudies-literature

Development of an Intermittent-Flow Enantioselective Aza-Henry Reaction Using an Arylnitromethane and Homogeneous Bronsted Acid-Base Catalyst with Recycle.

Project description:A stereoselective aza-Henry reaction between an arylnitromethane and Boc-protected aryl aldimine using a homogeneous Brønsted acid-base catalyst was translated from batch format to an automated intermittent-flow process. This work demonstrates the advantages of a novel intermittent-flow setup with product crystallization and slow reagent addition which is not amenable to the standard continuous equipment: plug flow tube reactor (PFR) or continuous stirred tank reactor (CSTR). A significant benefit of this strategy was the integration of an organocatalytic enantioselective reaction with straightforward product separation, including recycle of the catalyst, resulting in increased intensity of the process by maintaining high catalyst concentration in the reactor. A continuous campaign confirmed that these conditions could effectively provide high throughput of material using an automated system while maintaining high selectivity, thereby addressing nitroalkane safety and minimizing catalyst usage.

| S-EPMC4821467 | biostudies-literature

Chiral Bronsted acid from a cationic gold(I) complex: catalytic enantioselective protonation of silyl enol ethers of ketones.

Project description:A chiral Brønsted acid has been developed from a cationic gold(I) disphosphine complex in the presence of alcoholic solvent and applied to the enantioselective protonation reaction of silyl enol ethers of ketones. Various optically active cyclic ketones were obtained in excellent yields and high enantioselectivities, including cyclic ketones bearing aliphatic substrates at the α-position. Furthermore, the application of this Brønsted acid was extended to the first Brønsted acid-catalyzed enantioselective protonation reaction of silyl enol ethers of acyclic substrates, regardless of their E/Z ratio.

| S-EPMC3161142 | biostudies-literature

Development and mechanism of an enantioselective bromocycloetherification reaction via Lewis base/chiral Bronsted acid cooperative catalysis.

Project description:The development of a binary catalyst system for bromocycloetherification, consisting of an achiral Lewis base and a chiral Brønsted acid, is described in detail. The results of preliminary kinetic studies are also presented.

| S-EPMC4676414 | biostudies-literature

Enantioselective PCCP Bronsted acid-catalyzed aza-Piancatelli rearrangement.

Project description:An enantioselective aza-Piancatelli rearrangement has been developed using a chiral Brønsted acid based on pentacarboxycyclopentadiene (PCCP). This reaction provides rapid access to valuable chiral 4-amino-2-cyclopentenone building blocks from readily available starting material and is operationally simple.

| S-EPMC6633596 | biostudies-literature

Enantioselective PCCP Bronsted acid-catalyzed aminalization of aldehydes.

Project description:Here we present an enantioselective aminalization of aldehydes catalyzed by Brønsted acids based on pentacarboxycyclopentadienes (PCCPs). The cyclization reaction using readily available anthranilamides as building blocks provides access to valuable 2,3-dihydroquinazolinones containing one stereogenic carbon center with good enantioselectivity (ee up to 80%) and excellent yields (up to 97%).

| S-EPMC8450961 | biostudies-literature

Bronsted acid-catalysed enantioselective construction of axially chiral arylquinazolinones.

Project description:The axially chiral arylquinazolinone acts as a privileged structural scaffold, which is present in a large number of natural products and biologically active compounds as well as in chiral ligands. However, a direct catalytic enantioselective approach to access optically pure arylquinazolinones has been underexplored. Here we show a general and efficient approach to access enantiomerically pure arylquinazolinones in one-pot fashion catalysed by chiral phosphoric acids. A variety of axially chiral arylquinazolinones were obtained in high yields with good to excellent enantioselectivities under mild condition. Furthermore, we disclosed a method for atroposelective synthesis of alkyl-substituted arylquinazolinones involving Brønsted acid-catalysed carbon-carbon bond cleavage strategy. Finally, the asymmetric total synthesis of eupolyphagin bearing a cyclic arylquinazolinone skeleton was accomplished with an overall yield of 32% in six steps by utilizing the aforementioned methodology.

| S-EPMC5454535 | biostudies-literature

Enantioselective bromocycloetherification by Lewis base/chiral Bronsted acid cooperative catalysis.

Project description:A binary catalyst system for the enantioselective bromocycloetherification of 5-arylpentenols is described. The combination of an achiral Lewis base and a chiral Brønsted acid affords good enantioselectivities for the cyclization of Z configured 5-arylpentenols to form bromomethyltetrahydrofurans. The constitutional site selectivity is highly dependent upon the aromatic substituent and the configuration of the double bond.

| S-EPMC3238797 | biostudies-literature

Chiral Bronsted acid-catalyzed intramolecular S<sub>N</sub>2' reaction for enantioselective construction of a quaternary stereogenic center.

Project description:An enantioselective intramolecular anti-SN2' cyclization reaction for the construction of a quaternary stereogenic center was accomplished through the activation of the leaving group using a binaphthol-derived phosphoramide as the chiral Brønsted acid catalyst. The present allylic substitution reaction is beneficial not only for the regioselective nucleophilic substitution at the multi-substituted site of the double bond but also for controlling the stereochemical outcome because of using a geometrically defined double bond. Indeed, the reaction afforded synthetically useful amino alcohol derivatives having a tetra-substituted carbon center in a highly enantioselective manner in most cases, in which the modification of the sulfonamide unit of the phosphoramide catalyst was demonstrated to improve the enantioselectivity. Experimental and theoretical elucidation of the reaction mechanism suggested that the reaction proceeds through a synchronous anti-SN2' pathway, although NMR monitoring of the reaction indicated the formation of the phosphorimidate ester via the SN2 reaction of the catalyst with the substrate, which results in catalyst deactivation. Further theoretical studies of the origin of the stereochemical outcome at the generated quaternary stereogenic center were performed. Structural analysis of the transition states at the enantio-determining step revealed that the distinct discrimination of the substituents attached to the geometrically defined double bond is achieved by the anthryl and sulfonamide substituents of the catalyst through the three-point hydrogen bonding interactions and the T-shaped C-H···? interactions.

| S-EPMC6050593 | biostudies-literature

Chiral Bronsted acid-catalyzed enantioselective Friedel-Crafts reaction of 2-methoxyfuran with aliphatic ketimines generated <i>in situ</i>.

Project description:An enantioselective Friedel-Crafts reaction with aliphatic ketimines generated in situ from hemiaminal ethers catalyzed by a chiral Brønsted acid was investigated. The reaction of 2-methoxyfuran with (thio)hydantoin-derived hemiaminal methyl ether proceeded under the influence of a chiral phosphoric acid catalyst to afford the corresponding adduct possessing a quaternary stereogenic center in high yield with high enantioselectivity. Theoretical studies were also conducted to clarify the mechanism of the stereochemical outcome and the major factors contributing to the efficient enantioselection.

| S-EPMC5952551 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data