Browse
Submit Data
Databases
API
Help

Dataset Information

27 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

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

ABSTRACT: 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.

SUBMITTER: Denmark SE

PROVIDER: S-EPMC4676414 | biostudies-literature | 2014 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

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

Denmark Scott E SE Burk Matthew T MT

Chirality 20131107 7

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. ...[more]

PMID: 24395341

Similar Datasets

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

Lewis Base-Bronsted Acid-Enzyme Catalysis in Enantioselective Multistep One-Pot Syntheses.

Project description:Establishing one-pot, multi-step protocols combining different types of catalysts is one important goal for increasing efficiency in modern organic synthesis. In particular, the high potential of biocatalysts still needs to be harvested. Based on an in-depth mechanistic investigation of a new organocatalytic protocol employing two catalysts {1,4-diazabicyclo[2.2.2]octane (DABCO); benzoic acid (BzOH)}, a sequence was established providing starting materials for enzymatic refinement (ene reductase; alcohol dehydrogenase): A gram-scale access to a variety of enantiopure key building blocks for natural product syntheses was enabled utilizing up to six catalytic steps within the same reaction vessel.

| S-EPMC8360128 | biostudies-literature

Transition state analysis of enantioselective Bronsted base catalysis by chiral cyclopropenimines.

Project description:Experimental (13)C kinetic isotope effects have been used to interrogate the rate-limiting step of the Michael addition of glycinate imines to benzyl acrylate catalyzed by a chiral 2,3-bis(dicyclohexylamino) cyclopropenimine catalyst. The reaction is found to proceed via rate-limiting carbon-carbon bond formation. The origins of enantioselectivity and a key noncovalent CH···O interaction responsible for transition state organization are identified on the basis of density functional theory calculations and probed using experimental labeling studies. The resulting high-resolution experimental picture of the enantioselectivity-determining transition state is expected to guide new catalyst design and reaction development.

| S-EPMC4230825 | biostudies-literature

N-Heterocyclic Carbene and Chiral Bronsted Acid Cooperative Catalysis for a Highly Enantioselective [4+2] Annulation.

Project description:A chiral NHC/Brønsted acid cooperative catalysis system has been developed for asymmetric annulation of functionalized benzaldehydes and activated ketones through dearomative generation of dienolate.

| S-EPMC5496987 | biostudies-literature

Asymmetric cooperative catalysis of strong Bronsted acid-promoted reactions using chiral ureas.

Project description:Cationic organic intermediates participate in a wide variety of useful synthetic transformations, but their high reactivity can render selectivity in competing pathways difficult to control. Here, we describe a strategy for inducing enantioselectivity in reactions of protio-iminium ions, wherein a chiral catalyst interacts with the highly reactive intermediate through a network of noncovalent interactions. This interaction leads to an attenuation of the reactivity of the iminium ion and allows high enantioselectivity in cycloadditions with electron-rich alkenes (the Povarov reaction). A detailed experimental and computational analysis of this catalyst system has revealed the precise nature of the catalyst-substrate interactions and the likely basis for enantioinduction.

| S-EPMC2993568 | biostudies-literature

Enantioselective [2 + 2] Photocycloaddition via Iminium Ions: Catalysis by a Sensitizing Chiral Bronsted Acid.

Project description:N,O-Acetals derived from α,β-unsaturated β-aryl substituted aldehydes and (1-aminocyclohexyl)methanol were found to undergo a catalytic enantioselective [2 + 2] photocycloaddition to a variety of olefins (19 examples, 54-96% yield, 84-98% ee). The reaction was performed by visible light irradiation (λ = 459 nm). A chiral phosphoric acid (10 mol %) with an (R)-1,1'-bi-2-naphthol (binol) backbone served as the catalyst. The acid displays two thioxanthone groups attached to position 3 and 3' of the binol core via a meta-substituted phenyl linker. NMR studies confirmed the formation of an iminium ion which is attached to the acid counterion in a hydrogen-bond assisted ion pair. The catalytic activity of the acid rests on the presence of the thioxanthone moieties which enable a facile triplet energy transfer and an efficient enantioface differentiation.

| S-EPMC8251699 | biostudies-literature

Enantioselective conjugate additions of ?-amino radicals via cooperative photoredox and Lewis acid catalysis.

Project description:We report the highly enantioselective addition of photogenerated ?-amino radicals to Michael acceptors. This method features a dual-catalyst protocol that combines transition metal photoredox catalysis with chiral Lewis acid catalysis. The combination of these two powerful modes of catalysis provides an effective, general strategy to generate and control the reactivity of photogenerated reactive intermediates.

| S-EPMC4547529 | biostudies-literature

N-Heterocyclic carbenes as chiral Bronsted base catalysts: a highly diastereo- and enantioselective 1,6-addition reaction.

Project description:Highly diastereo- and enantioselective 1,6-addition of 1,3-ketoamides to p-quinone methides (p-QMs) using chiral NHCs as Brønsted base catalysts is developed. The reaction is based on the utilization of a 1,3-ketoamide having acidic N-H that forms a chiral ion-pair consisting of the enolate and the azolium ion. Different ?-ketoamides and functionalized p-QMs are applicable to the reaction. Synthetic application of the method is demonstrated via the preparation of highly enantioenriched ? and ?-lactam derivatives.

| S-EPMC6144034 | 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 Tandem Cyclization of Alkyne-Tethered Indoles Using Cooperative Silver(I)/Chiral Phosphoric Acid Catalysis.

Project description:Reported is the enantioselective synthesis of tetracyclic indolines using silver(I)/chiral phosphoric acid catalysis. A variety of alkyne-tethered indoles are suitable for this process. Mechanistic studies suggest that the in?situ generated silver(I) chiral phosphate activates both the alkyne and the indole nucleophile in the initial cyclization step through an intermolecular hydrogen bond and the phosphate anion promotes proton transfer. In addition, further modifications of the cyclization products enabled stereochemistry-function studies of a series of bioactive indolines.

| S-EPMC5997581 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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