Browse
Submit Data
Databases
API
Help

Dataset Information

16 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Asymmetric Oxidative Coupling of Phenols and Hydroxycarbazoles.

ABSTRACT: The first examples of asymmetric oxidative coupling of simple phenols and 2-hydroxycarbazoles are outlined. Generation of a more vanadium catalyst by ligand design and by addition of an exogenous Brønsted or Lewis acid was found to be key to coupling the more oxidatively resistant phenols. The resultant vanadium complex is both more Lewis acidic and more strongly oxidizing. Good to excellent levels of enantioselectivity could be obtained, and simple trituration readily provided the products with ?95% ee.

SUBMITTER: Kang H

PROVIDER: S-EPMC5654492 | biostudies-literature | 2017 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Asymmetric Oxidative Coupling of Phenols and Hydroxycarbazoles.

Kang Houng H Lee Young Eun YE Reddy Peddiahgari Vasu Govardhana PVG Dey Sangeeta S Allen Scott E SE Niederer Kyle A KA Sung Paul P Hewitt Kirsten K Torruellas Carilyn C Herling Madison R MR Kozlowski Marisa C MC

Organic letters 20171012 20

The first examples of asymmetric oxidative coupling of simple phenols and 2-hydroxycarbazoles are outlined. Generation of a more vanadium catalyst by ligand design and by addition of an exogenous Brønsted or Lewis acid was found to be key to coupling the more oxidatively resistant phenols. The resultant vanadium complex is both more Lewis acidic and more strongly oxidizing. Good to excellent levels of enantioselectivity could be obtained, and simple trituration readily provided the products with ...[more]

PMID: 29022352

Similar Datasets

Sulfoxide-mediated oxidative cross-coupling of phenols.

Project description:A metal-free, oxidative coupling of phenols with various nucleophiles, including arenes, 1,3-diketones and other phenols, is reported. Cross-coupling is mediated by a sulfoxide which inverts the reactivity of the phenol partner. Crucially, the process shows high selectivity for cross-versus homo-coupling and allows efficient access to a variety of aromatic scaffolds including biaryls, benzofurans and, through an iterative procedure, aromatic oligomers.

| S-EPMC8150100 | biostudies-literature

Oxidative Photocatalytic Homo- and Cross-Coupling of Phenols: Nonenzymatic, Catalytic Method for Coupling Tyrosine.

Project description:The oxidative photocatalytic method for phenol-phenol homo-coupling and cross-coupling is described and isolated yields of 16-97% are obtained. Measured oxidation potentials and computed nucleophilicity parameters support a mechanism of nucleophilic attack of one partner onto the oxidized neutral radical form of the other partner. Understanding of this model permitted development of cross-coupling reactions between nucleophilic phenols/arenes and easily oxidized phenols with high selectivity and efficiency. A highlight of this method is that one equivalent of each coupling partner is utilized. Building on these findings, a non-enzymatic, catalytic method for coupling tyrosine was also developed.

| S-EPMC8078885 | biostudies-literature

Selective oxidative homo- and cross-coupling of phenols with aerobic catalysts.

Project description:Simple catalysts that use atom-economical oxygen as the terminal oxidant to accomplish selective ortho-ortho, ortho-para, or para-para homo-couplings of phenols are described. In addition, chromium salen catalysts have been discovered as uniquely effective in the cross-coupling of different phenols with high chemo- and regioselectivity.

| S-EPMC4227839 | biostudies-literature

Vanadium-Catalyzed Oxidative Intramolecular Coupling of Tethered Phenols: Formation of Phenol-Dienone Products.

Project description:A mild and efficient method for the vanadium-catalyzed intramolecular coupling of tethered free phenols is described. The corresponding phenol-dienone products are prepared directly in good yields with low catalyst loadings. Electronically diverse tethered phenol precursors are well tolerated, and the catalytic method was effectively applied as the key step in syntheses of three natural products and a synthetically useful morphinan alkaloid precursor.

| S-EPMC7314600 | biostudies-literature

Visible-Light-Induced Oxidative Coupling of Phenols and Alkenylphenols with a Recyclable, Solid Photocatalyst.

Project description:A photocatalytic method for phenol and alkenylphenol oxidative coupling is reported using an inexpensive heterogeneous titanium dioxide photocatalyst with air and visible light. During the coupling process, the Ti-substrate complex is activated under visible light through a ligand to metal charge transfer effect, and the diphenol adduct is proposed to form through a radical cation. The heterogeneous TiO2 catalyst remains stable throughout the reaction and can be easily removed and reused multiple times.

| S-EPMC10015407 | biostudies-literature

Mechanistic Insights into the FeCl3-Catalyzed Oxidative Cross-Coupling of Phenols with 2-Aminonaphthalenes.

Project description:The selective FeCl3-catalyzed oxidative cross-coupling reaction between phenols and primary, secondary, and tertiary 2-aminonaphthalene derivatives was investigated. The generality of this scalable method provides a sustainable alternative for preparing N,O-biaryl compounds that are widely used as ligands and catalysts. Based on a comprehensive kinetic investigation, a catalytic cycle involving a ternary complex that binds to both the coupling partners and the oxidant during the key oxidative coupling step is postulated. Furthermore, the studies showed that the reaction is regulated by off-cycle acid-base and ligand exchange processes.

| S-EPMC7783733 | biostudies-literature

Organocatalytic asymmetric formal oxidative coupling for the construction of all-aryl quaternary stereocenters.

Project description:A new catalytic asymmetric formal cross dehydrogenative coupling process for the construction of all-aryl quaternary stereocenters is disclosed, which provides access to rarely explored chiral tetraarylmethanes with excellent enantioselectivity. The suitable oxidation conditions and the hydrogen-bond-based organocatalysis have enabled efficient intermolecular C-C bond formation in an overwhelmingly crowded environment under mild conditions. para-Quinone methides bearing an ortho-directing group serve as the key intermediate. The precise loading of DDQ is critical to the high enantioselectivity. The chiral products have also been demonstrated as promising antiviral agents.

| S-EPMC8442720 | biostudies-literature

First Evidence of Pheomelanin-UVA-Driven Synthesis of Pummerer's Ketones by Peroxidase-Mediated Oxidative Coupling of Substituted Phenols.

Project description:Photoexcitation of pheomelanin produces high-energy singlet oxygen and the superoxide anion, which are reactive species in damage of cellular targets. In principle, these species can be involved in processes of synthetic utility when adequate experimental conditions are defined. Here, we describe that pheomelanin performs as a selective UVA antenna for the horseradish peroxidase oxidative coupling of substituted phenols to biologically active Pummerer's ketones under 2-methyltetrahydrofuran/buffer biphasic conditions. In this system, singlet oxygen is scavenged by conversion of 2-methyltetrahydrofuran into the corresponding organic hydroperoxide, while the superoxide anion is dismutated into hydrogen peroxide. Both these intermediates are able to oxidize the active site of horseradish peroxidase triggering the oxidative coupling reaction. Trimer derivatives, produced by addition of phenoxy radicals on preformed Pummerer's ketones were also isolated, suggesting the possibility to further improve the structural complexity of the reaction products.

| S-EPMC9753113 | biostudies-literature

Aerobic Catalyzed Oxidative Cross-Coupling of N,N-Disubstituted Anilines and Aminonaphthalenes with Phenols and Naphthols.

Project description:The cross-coupling of N,N-dialkyl aniline and aminonaphthalenes with phenols and naphthols using a Cr-salen catalyst under aerobic conditions was developed. Notably, air serves as an effective oxidant affording products in high selectivity. Initial mechanistic studies suggest an outer-sphere oxidation of the aniline/aminonaphthalene partner, followed by nucleophilic attack of the phenol/naphthol. Single products were observed in most cases, whereas mixtures of C-C and C-O coupled products arose from reactions involving aminonapthalene and sterically unencumbered phenols.

| S-EPMC7060808 | biostudies-literature

Asymmetric Synthesis of Gonytolide A: Strategic Use of an Aryl Halide Blocking Group for Oxidative Coupling.

Project description:The first synthesis of the chromanone lactone dimer gonytolide A has been achieved employing vanadium(V)-mediated oxidative coupling of the monomer gonytolide C. An o-bromine blocking group strategy was employed to favor para- para coupling and to enable kinetic resolution of (±)-gonytolide C. Asymmetric conjugate reduction enabled practical kinetic resolution of a chiral, racemic precursor and the asymmetric synthesis of (+)-gonytolide A and its atropisomer.

| S-EPMC5943148 | 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