Browse
Submit Data
Databases
API
Help

Dataset Information

30 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Engaging Alkenyl Halides with Alkylsilicates via Photoredox Dual Catalysis.

ABSTRACT: Single-electron transmetalation via photoredox/nickel dual catalysis provides the opportunity for the construction of Csp(3)-Csp(2) bonds through the transfer of alkyl radicals under very mild reaction conditions. A general procedure for the cross-coupling of primary and secondary (bis-catecholato)alkylsilicates with alkenyl halides is presented. The developed method allows not only alkenyl bromides and iodides but also previously underexplored alkenyl chlorides to be employed.

SUBMITTER: Patel NR

PROVIDER: S-EPMC4854195 | biostudies-literature | 2016 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Engaging Alkenyl Halides with Alkylsilicates via Photoredox Dual Catalysis.

Patel Niki R NR Kelly Christopher B CB Jouffroy Matthieu M Molander Gary A GA

Organic letters 20160201 4

Single-electron transmetalation via photoredox/nickel dual catalysis provides the opportunity for the construction of Csp(3)-Csp(2) bonds through the transfer of alkyl radicals under very mild reaction conditions. A general procedure for the cross-coupling of primary and secondary (bis-catecholato)alkylsilicates with alkenyl halides is presented. The developed method allows not only alkenyl bromides and iodides but also previously underexplored alkenyl chlorides to be employed. ...[more]

PMID: 26828317

Similar Datasets

Phenol Derivatives as Coupling Partners with Alkylsilicates in Photoredox/Nickel Dual Catalysis.

Project description:Photoredox/nickel dual catalysis via single electron transmetalation allows coupling of Csp(3)-Csp(2) hybridized centers under mild conditions. A procedure for the coupling of electron-deficient aryl triflates, -tosylates, and -mesylates with alkylbis(catecholato)silicates is presented. This method represents the first example of the use of phenol derivatives as electrophilic coupling partners in photoredox/nickel dual catalysis.

| S-EPMC4994714 | biostudies-literature

Engaging sulfinate salts via Ni/photoredox dual catalysis enables facile Csp2 -SO2R coupling.

Project description:This report details the development and implementation of a strategy to construct aryl- and heteroaryl sulfones via Ni/photoredox dual catalysis. Using aryl sulfinate salts, the C-S bond can be forged at room temperature under base-free conditions. An array of aryl- and heteroaryl halides are compatible with this approach. The broad tolerance and mild nature of the described reaction could potentially be employed to prepare sulfones with biological relevance (e.g., in bioconjugation, drug substance synthesis, etc.) as demonstrated in the synthesis of drug-like compounds or their precursors. When paired with existing Ni/photoredox chemistry for Csp3 -Csp2 cross-coupling, an array of diverse sulfone scaffolds can be readily assembled from bifunctional electrophiles. A mechanistic manifold consistent with experimental and computational data is presented.

| S-EPMC5916223 | biostudies-literature

Enantioselective Electroreductive Coupling of Alkenyl and Benzyl Halides via Nickel Catalysis.

Project description:An electrochemically-driven enantioselective nickel-catalyzed reductive cross-coupling of alkenyl bromides and benzyl chlorides is reported. The reaction forms products bearing allylic stereogenic centers with good enantioselectivity under mild conditions in an undivided cell. Electrochemical activation and turnover of the catalyst mitigate issues posed by metal powder reductants. This report demonstrates that enantioselective Ni-catalyzed cross-electrophile couplings can be driven electrochemically.

| S-EPMC7190267 | biostudies-literature

Thioetherification via Photoredox/Nickel Dual Catalysis.

Project description:Hypervalent alkylsilicates represent new and readily accessible precursors for the generation of alkyl radicals under photoredox conditions. Alkyl radicals generated from such silicates serve as effective hydrogen atom abstractors from thiols, furnishing thiyl radicals. The reactive sulfur species generated in this manner can be funneled into a nickel-mediated cross-coupling cycle employing aromatic bromides to furnish thioethers. The serendipitous discovery of this reaction and its utilization for the thioetherification of various aryl and heteroaryl bromides with a diverse array of thiols is described. The S-H selective H atom abstraction event enables a wide range of functional groups, including those bearing protic moieties, to be tolerated.

| S-EPMC4854196 | biostudies-literature

Dual catalysis. Merging photoredox with nickel catalysis: coupling of α-carboxyl sp³-carbons with aryl halides.

Project description:Over the past 40 years, transition metal catalysis has enabled bond formation between aryl and olefinic (sp(2)) carbons in a selective and predictable manner with high functional group tolerance. Couplings involving alkyl (sp(3)) carbons have proven more challenging. Here, we demonstrate that the synergistic combination of photoredox catalysis and nickel catalysis provides an alternative cross-coupling paradigm, in which simple and readily available organic molecules can be systematically used as coupling partners. By using this photoredox-metal catalysis approach, we have achieved a direct decarboxylative sp(3)-sp(2) cross-coupling of amino acids, as well as α-O- or phenyl-substituted carboxylic acids, with aryl halides. Moreover, this mode of catalysis can be applied to direct cross-coupling of C(sp³)-H in dimethylaniline with aryl halides via C-H functionalization.

| S-EPMC4296524 | biostudies-literature

Aminomethylation of Aryl Halides using α-Silylamines Enabled by Ni/Photoredox Dual Catalysis.

Project description:A protocol for the aminomethylation of aryl halides using α-silylamines via Ni/photoredox dual catalysis is described. The low oxidation potential of these silylated species enables facile single electron transfer (SET) oxidation of the amine followed by rapid desilylation. The resulting α-amino radicals can be directly funneled into a nickel-mediated cross-coupling cycle with aryl halides. The process accomplishes aminomethylation under remarkably mild conditions and tolerates numerous aryl- and heteroaryl halides with an array of functional groups.

| S-EPMC5771658 | biostudies-literature

Nickel/Photoredox-Catalyzed Amidation via Alkylsilicates and Isocyanates.

Project description:A nickel/photoredox, dual-catalyzed amidation reaction between alkylsilicate reagents and alkyl/aryl isocyanates is reported. In contrast to the previously reported reductive coupling process, this protocol is characterized by mild reaction conditions and the absence of a stoichiometric reductant. A mechanistic hypothesis involving a nickel-isocyanate adduct is proposed based on literature precedent and further validation by experimental results.

| S-EPMC5784433 | biostudies-literature

Metalated aziridines for cross-coupling with aryl and alkenyl halides via palladium catalysis.

Project description:The palladium-catalyzed coupling of an aziridinylzinc chloride intermediate with alkenyl and aryl halides has been demonstrated. The method provides products with retention of aziridine stereochemistry. The utility of the coupling procedure is illustrated in the synthesis of structures related to l-furanomycin.

| S-EPMC2996137 | biostudies-literature

Haloselective Cross-Coupling via Ni/Photoredox Dual Catalysis.

Project description:The chemoselective functionalization of polyfunctional aryl linchpins is crucial for rapid diversification. Although well-explored for Csp2 and Csp nucleophiles, the chemoselective introduction of Csp3 groups remains notoriously difficult and is virtually undocumented using Ni catalysts. To fill this methodological gap, a "haloselective" cross-coupling process of arenes bearing two halogens, I and Br, using ammonium alkylbis(catecholato)silicates, has been developed. Utilizing Ni/photoredox dual catalysis, Csp3 -Csp2 bonds can be forged selectively at the iodine-bearing carbon of bromo(iodo)arenes. The described high-yielding, base-free strategy accommodates various protic functional groups. Selective electrophile activation enables installation of a second Csp3 center and can be done without the need for purification of the intermediate monoalkylated product.

| S-EPMC5548095 | biostudies-literature

Base-Free Photoredox/Nickel Dual-Catalytic Cross-Coupling of Ammonium Alkylsilicates.

Project description:Single-electron transmetalation is recognized as an enabling technology for the mild transfer of alkyl groups to transition metal catalysts in cross-coupling reactions. Hypercoordinate silicates represent a new and improved class of radical precursors because of their low oxidation potentials and the innocuous byproducts generated upon oxidation. Herein, we report the cross-coupling of secondary and primary ammonium alkylsilicates with (hetero)aryl bromides in good to excellent yields. The base-free conditions have exceptional protic group tolerance on both partners, permitting the cross-coupling of unprotected primary and secondary amines.

| S-EPMC4854202 | 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