Browse
Submit Data
Databases
API
Help

Dataset Information

44 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Direct ?-functionalization of cyclic ketones with aryl ketones via the merger of photoredox and organocatalysis.

ABSTRACT: The direct ?-coupling of cyclic ketones with aryl ketones has been achieved via the synergistic combination of photoredox catalysis and organocatalysis. Diaryl oxymethyl or aryl-alkyl oxymethyl radicals, transiently generated via single-electron reduction of ketone precursors, readily merge with ?-enaminyl radical species, generated by photon-induced enamine oxidation, to produce ?-hydroxyketone adducts. Experimental evidence indicates that two discrete reaction pathways can be operable in this process depending upon the nature of the ketyl radical precursor and the photocatalyst.

SUBMITTER: Petronijevic FR

PROVIDER: S-EPMC3934322 | biostudies-literature | 2013 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Direct β-functionalization of cyclic ketones with aryl ketones via the merger of photoredox and organocatalysis.

Petronijević Filip R FR Nappi Manuel M MacMillan David W C DW

Journal of the American Chemical Society 20131122 49

The direct β-coupling of cyclic ketones with aryl ketones has been achieved via the synergistic combination of photoredox catalysis and organocatalysis. Diaryl oxymethyl or aryl-alkyl oxymethyl radicals, transiently generated via single-electron reduction of ketone precursors, readily merge with β-enaminyl radical species, generated by photon-induced enamine oxidation, to produce γ-hydroxyketone adducts. Experimental evidence indicates that two discrete reaction pathways can be operable in this ...[more]

PMID: 24237366

Similar Datasets

Direct β-alkylation of aldehydes via photoredox organocatalysis.

Project description:Direct β-alkylation of saturated aldehydes has been accomplished by synergistically combining photoredox catalysis and organocatalysis. Photon-induced enamine oxidation provides an activated β-enaminyl radical intermediate, which readily combines with a wide range of Michael acceptors to produce β-alkyl aldehydes in a highly efficient manner. Furthermore, this redox-neutral, atom-economical C-H functionalization protocol can be achieved both inter- and intramolecularly. Mechanistic studies by various spectroscopic methods suggest that a reductive quenching pathway is operable.

| S-EPMC4333594 | biostudies-literature

Activation of C-H bonds via the merger of photoredox and organocatalysis: a coupling of benzylic ethers with Schiff bases.

Project description:The photoredox-mediated coupling of benzylic ethers with Schiff bases has been accomplished. Direct benzylic C-H activation by a combination of a thiol catalyst with an iridium photocatalyst and subsequent radical-radical coupling with secondary aldimines affords a variety of ?-amino ether products in good to excellent yields. Mechanistic studies suggest that a reductive quenching pathway of the photocatalyst is operable.

| S-EPMC4277755 | biostudies-literature

Enantioselective ?-benzylation of aldehydes via photoredox organocatalysis.

Project description:The first enantioselective aldehyde ?-benzylation using electron-deficient aryl and heteroaryl substrates has been accomplished. The productive merger of a chiral imidazolidinone organocatalyst and a commercially available iridium photoredox catalyst in the presence of household fluorescent light directly affords the desired homobenzylic stereogenicity in good to excellent yield and enantioselectivity. The utility of this methodology has been demonstrated via rapid access to an enantioenriched drug target for angiogenesis suppression.

| S-EPMC3056320 | biostudies-literature

Enantioselective alpha-trifluoromethylation of aldehydes via photoredox organocatalysis.

Project description:The first enantioselective, organocatalytic alpha-trifluoromethylation and alpha-perfluoroalkylation of aldehydes have been accomplished using a readily available iridium photocatalyst and a chiral imidazolidinone catalyst. A range of alpha-trifluoromethyl and alpha-perfluoroalkyl aldehydes were obtained from commercially available perfluoroalkyl halides with high efficiency and enantioselectivity. The resulting alpha-trifluoromethyl aldehydes were subsequently shown to be versatile precursors for the construction of a variety of enantioenriched trifluoromethylated building blocks.

| S-EPMC3310169 | biostudies-literature

Enantioselective aerobic oxidative cross-dehydrogenative coupling of glycine derivatives with ketones and aldehydes <i>via</i> cooperative photoredox catalysis and organocatalysis.

Project description:The combination of photoredox catalysis and enamine catalysis has enabled the development of an enantioselective aerobic oxidative cross-dehydrogenative coupling between glycine derivatives and simple ketones or aldehydes, which provides an efficient approach for the rapid synthesis of enantiopure unnatural α-alkyl α-amino acid derivatives in good yield with excellent diastereo- (up to >99 : 1) and enantioselectivities (up to 97% ee). This process includes the direct photoinduced oxidation of glycine derivatives to an imine intermediate, followed by the asymmetric Mannich-type reaction with an enamine intermediate generated in situ from a ketone or aldehyde and a chiral secondary amine organocatalyst. This mild method allows the direct formation of a C-C bond with simultaneous installation of two new stereocenters without wasteful removal of functional groups.

| S-EPMC8159221 | biostudies-literature

Predictive Model for Site-Selective Aryl and Heteroaryl C-H Functionalization via Organic Photoredox Catalysis.

Project description:Direct C-H functionalization of aromatic compounds is a useful synthetic strategy that has garnered much attention because of its application to pharmaceuticals, agrochemicals, and late-stage functionalization reactions on complex molecules. On the basis of previous methods disclosed by our lab, we sought to develop a predictive model for site selectivity and extend this aryl functionalization chemistry to a selected set of heteroaromatic systems commonly used in the pharmaceutical industry. Using electron density calculations, we were able to predict the site selectivity of direct C-H functionalization in a number of heterocycles and identify general trends observed across heterocycle classes.

| S-EPMC5996966 | biostudies-literature

Synthesis of cyclic enones via direct palladium-catalyzed aerobic dehydrogenation of ketones.

Project description:α,β-Unsaturated carbonyl compounds are versatile intermediates in the synthesis of pharmaceuticals and biologically active compounds. Here, we report the discovery and application of Pd(DMSO)(2)(TFA)(2) as a catalyst for direct dehydrogenation of cyclohexanones and other cyclic ketones to the corresponding enones, using O(2) as the oxidant. The substrate scope includes heterocyclic ketones and several natural-product precursors.

| S-EPMC3173566 | biostudies-literature

Enantioselective α-arylation of aldehydes via the productive merger of iodonium salts and organocatalysis.

Project description:The enantioselective α-arylation of aldehydes has been accomplished using diaryliodonium salts and a combination of copper and organic catalysts. These mild catalytic conditions provide a new strategy for the enantioselective construction and retention of enolizable α-formyl benzylic stereocenters, a valuable synthon for the production of medicinal agents. As one example, this new asymmetric protocol has been applied to the rapid synthesis of (S)-ketoprofen, a commercially successful oral and topical analgesic.

| S-EPMC3082494 | biostudies-literature

C-H functionalization of amines with aryl halides by nickel-photoredox catalysis.

Project description:We describe the functionalization of α-amino C-H bonds with aryl halides using a combination of nickel and photoredox catalysis. This direct C-H, C-X coupling uses inexpensive and readily available starting materials to generate benzylic amines, an important class of bioactive molecules. Mechanistically, this method features the direct arylation of α-amino radicals mediated by a nickel catalyst. This reactivity is demonstrated for a range of aryl halides and N-aryl amines, with orthogonal scope to existing C-H activation and photoredox methodologies. We also report reactions with several complex aryl halides, demonstrating the potential utility of this approach in late-stage functionalization.

| S-EPMC5207500 | biostudies-literature

Photoredox activation for the direct β-arylation of ketones and aldehydes.

Project description:The direct β-activation of saturated aldehydes and ketones has long been an elusive transformation. We found that photoredox catalysis in combination with organocatalysis can lead to the transient generation of 5π-electron β-enaminyl radicals from ketones and aldehydes that rapidly couple with cyano-substituted aryl rings at the carbonyl β-position. This mode of activation is suitable for a broad range of carbonyl β-functionalization reactions and is amenable to enantioselective catalysis.

| S-EPMC3723331 | 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