Browse
Submit Data
Databases
API
Help

Dataset Information

19 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Catalytic Alkene Difunctionalization via Imidate Radicals.

ABSTRACT: The first catalytic strategy to harness imidate radicals has been developed. This approach enables alkene difunctionalization of allyl alcohols by photocatalytic reduction of their oxime imidates. The ensuing imidate radicals undergo consecutive intra- and intermolecular reactions to afford (i) hydroamination, (ii) aminoalkylation, or (iii) aminoarylation, via three distinct radical mechanisms. The broad scope and utility of this catalytic method for imidate radical reactivity is presented, along with comparisons to other N-centered radicals and complementary, closed-shell imidate pathways.

SUBMITTER: Nakafuku KM

PROVIDER: S-EPMC6519729 | biostudies-literature | 2018 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Catalytic Alkene Difunctionalization via Imidate Radicals.

Nakafuku Kohki M KM Fosu Stacy C SC Nagib David A DA

Journal of the American Chemical Society 20180829 36

The first catalytic strategy to harness imidate radicals has been developed. This approach enables alkene difunctionalization of allyl alcohols by photocatalytic reduction of their oxime imidates. The ensuing imidate radicals undergo consecutive intra- and intermolecular reactions to afford (i) hydroamination, (ii) aminoalkylation, or (iii) aminoarylation, via three distinct radical mechanisms. The broad scope and utility of this catalytic method for imidate radical reactivity is presented, alon ...[more]

PMID: 30156404

Similar Datasets

Mechanochemistry Drives Alkene Difunctionalization via Radical Ligand Transfer and Electron Catalysis.

Project description:A general and modular protocol is reported for olefin difunctionalization through mechanochemistry, facilitated by cooperative radical ligand transfer (RLT) and electron catalysis. Utilizing mechanochemical force and catalytic amounts of 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO), ferric nitrate can leverage nitryl radicals, transfer nitrooxy-functional group via RLT, and mediate an electron catalysis cycle under room temperature. A diverse range of activated and unactivated alkenes exhibited chemo- and regioselective 1,2-nitronitrooxylation under solvent-free or solvent-less conditions, showcasing excellent functional group tolerance. Mechanistic studies indicated a significant impact of mechanochemistry and highlighted the radical nature of this nitrative difunctionalization process.

| S-EPMC11304296 | biostudies-literature

Alkene 1,2-Difunctionalization by Radical Alkenyl Migration.

Project description:Transition-metal-free radical ?-perfluoroalkylation with the accompanying vicinal ?-alkenylation of unactivated alkenes is presented. These radical cascades proceed by means of 1,4- or 1,5-alkenyl migration by electron catalysis on readily accessed allylic alcohols. The reactions comprise a regioselective perfluoroalkyl radical addition with subsequent alkenyl migration and concomitant deprotonation to generate a ketyl radical anion that sustains the chain as a single-electron-transfer reducing reagent.

| S-EPMC5838557 | biostudies-other

Pd-Catalyzed Alkene Difunctionalization Reactions of Malonate Nucleophiles: Synthesis of Substituted Cyclopentanes via Alkene Aryl-Alkylation and Akenyl-Alkylation.

Project description:The Pd-catalyzed coupling of malonate nucleophiles with alkenes bearing tethered aryl or alkenyl triflates is described. These alkene difunctionalization reactions afford malonate-substituted cyclopentanes that contain fused aryl or cycloalkenyl rings. The transformations generate a five-membered ring, two C-C bonds, and provide products bearing up to three stereocenters with good chemical yield and generally high diastereoselectivity.

| S-EPMC6996780 | biostudies-literature

Catalytic β C-H amination <i>via</i> an imidate radical relay.

Project description:The first catalytic strategy to harness imidate radicals for C-H functionalization has been developed. This iodine-catalyzed approach enables β C-H amination of alcohols by an imidate-mediated radical relay. In contrast to our first-generation, (super)stoichiometric protocol, this catalytic method enables faster and more efficient reactivity. Furthermore, lower oxidant concentration affords broader functional group tolerance, including alkenes, alkynes, alcohols, carbonyls, and heteroarenes. Mechanistic experiments interrogating the electronic nature of the key 1,5 H-atom transfer event are included, as well as probes for chemo-, regio-, and stereo-selectivity.

| S-EPMC6419930 | biostudies-literature

Catalytic 1,3-Difunctionalization via Oxidative C-C Bond Activation.

Project description:Electronegative substituents arrayed in 1,3-relationships along saturated carbon frameworks can exert strong influence over molecular conformation due to dipole minimization effects. Simple and general methods for incorporation of such functional group relationships could thus provide a valuable tool for modulating molecular shape. Here, we describe a general strategy for the 1,3-oxidation of cyclopropanes using aryl iodine(I-III) catalysis, with emphasis on 1,3-difluorination reactions. These reactions make use of practical, commercially available reagents and can engage a variety of substituted cyclopropane substrates. Analysis of crystal and solution structures of several of the products reveal the consistent effect of 1,3-difluorides in dictating molecular conformation. The generality of the 1,3-oxidation strategy is demonstrated through the catalytic oxidative ring-opening of cyclopropanes for the synthesis of 1,3-fluoroacetoxylated products, 1,3-diols, 1,3-amino alcohols, and 1,3-diamines.

| S-EPMC5671765 | biostudies-literature

Tandem copper and photoredox catalysis in photocatalytic alkene difunctionalization reactions.

Project description:Oxidative alkene difunctionalization reactions are important in synthetic organic chemistry because they can install polar functional groups onto simple non-polar alkene moieties. Many of the most common methods for these reactions rely upon the reactivity of pre-oxidized electrophilic heteroatom donors that can often be unstable, explosive, or difficult to handle. Herein, we describe a method for alkene oxyamination and diamination that utilizes simple carbamate and urea groups as nucleophilic heteroatom donors. This method uses a tandem copper-photoredox catalyst system that is operationally convenient. The identity of the terminal oxidant is critical in these studies. Ag(I) salts proved to be unique in their ability to turn over the copper cocatalyst without deleteriously impacting the reactivity of the organoradical intermediates.

| S-EPMC6369989 | biostudies-literature

Umpolung Difunctionalization of Carbonyls via Visible-Light Photoredox Catalytic Radical-Carbanion Relay.

Project description:The combination of photoredox catalysis with the Wolff-Kishner (WK) reaction allows the difunctionalization of carbonyl groups by a radical-carbanion relay sequence (photo-Wolff-Kishner reaction). Photoredox initiated radical addition to N-sulfonylhydrazones yields ?-functionalized carbanions following the WK-type mechanism. With sulfur-centered radicals, the carbanions are further functionalized by reaction with electrophiles including CO2 and aldehydes, whereas CF3 radical addition furnishes a wide range of gem-difluoroalkenes through ?-fluoride elimination of the generated ?-CF3 carbanions. More than 80 substrate examples demonstrate the broad applicability of this reaction sequence. A series of investigations including radical inhibition, deuterium labeling, fluorescence quenching, cyclic voltammetry, and control experiments support the proposed radical-carbanion relay mechanism.

| S-EPMC7252948 | biostudies-literature

Use of aryl chlorides as electrophiles in Pd-catalyzed alkene difunctionalization reactions.

Project description:The development of conditions that allow use of inexpensive aryl chlorides as electrophiles in Pd-catalyzed alkene carboamination and carboetherification reactions is described. A catalyst composed of Pd(OAc)(2) and S-Phos minimizes N-arylation of the substrate and prevents formation of mixtures of regioisomeric products. A number of heterocycles, including pyrrolidines, isoxazolidines, tetrahydrofurans, and pyrazolidines, are efficiently generated with this method.

| S-EPMC2853027 | biostudies-literature

Advancing the mechanistic understanding of an enantioselective palladium-catalyzed alkene difunctionalization reaction.

Project description:The mechanism of an enantioselective palladium-catalyzed alkene difunctionalization reaction has been investigated. Kinetic analysis provides evidence of turnover-limiting attack of a proposed quinone methide intermediate with MeOH and suggests that copper is involved in productive product formation, not just catalyst turnover. Through examination of substrate electronic effects, a Jaffé relationship was observed correlating rate to electronic perturbation at two positions of the substrate. Ligand effects were evaluated to provide evidence of rapid ligand exchange between palladium and copper as well as a correlation between ligand electronic nature and enantioselectivity.

| S-EPMC3066298 | biostudies-literature

Pd-Catalyzed Alkene Difunctionalization Reactions of Enolates for the Synthesis of Substituted Bicyclic Cyclopentanes.

Project description:Palladium-catalyzed alkene difunctionalization reactions between alkenes bearing tethered aryl or alkenyl triflates and enolate nucleophiles are described. The transformations form two C-C bonds, a ring, and up to two stereocenters, while producing substituted cyclopentane derivatives that contain appended carbonyl functionality. Products are formed with up to >20:1 diastereoselectivity, and formation of sterically congested bonds between quaternary carbon atoms is feasible.

| S-EPMC7886259 | 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