Browse
Submit Data
Databases
API
Help

Dataset Information

21 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Coupling of Alternating Current to Transition-Metal Catalysis: Examples of Nickel-Catalyzed Cross-Coupling.

ABSTRACT: The coupling of transition-metal to photoredox catalytic cycles through single-electron transfer steps has become a powerful tool in the development of catalytic processes. In this work, we demonstrated that transition-metal catalysis can be coupled to alternating current (AC) through electron transfer steps that occur periodically at the same electrode. AC-assisted Ni-catalyzed amination, etherification, and esterification of aromatic bromides showed higher yields and selectivity compared to that observed in the control experiments with direct current. Our mechanistic studies suggested the importance of both reduction and oxidation processes in the maintenance of the AC-assisted catalytic reactions. As described in presented examples, the AC assistance should be well-suited for catalytic cycles involving reductive elimination or oxidative addition as a limiting step.

SUBMITTER: Bortnikov EO

PROVIDER: S-EPMC7783731 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Coupling of Alternating Current to Transition-Metal Catalysis: Examples of Nickel-Catalyzed Cross-Coupling.

Bortnikov Evgeniy O EO Semenov Sergey N SN

The Journal of organic chemistry 20201113 1

The coupling of transition-metal to photoredox catalytic cycles through single-electron transfer steps has become a powerful tool in the development of catalytic processes. In this work, we demonstrated that transition-metal catalysis can be coupled to alternating current (AC) through electron transfer steps that occur periodically at the same electrode. AC-assisted Ni-catalyzed amination, etherification, and esterification of aromatic bromides showed higher yields and selectivity compared to th ...[more]

PMID: 33186048

Similar Datasets

Photoredox Catalysis Unlocks Single-Electron Elementary Steps in Transition Metal Catalyzed Cross-Coupling.

Project description:Since initial reports, cross-coupling technologies employing photoredox catalysts to access novel reactivity have developed with increasing pace. In this Outlook, prominent examples from the recent literature are organized on the basis of the elementary transformation enabled by photoredox catalysis and are discussed in the context of relevant historical precedent in stoichiometric organometallic chemistry. This treatment allows mechanistic similarities inherent to odd-electron transition metal reactivity to be generalized to a set of lessons for future reaction development.

| S-EPMC4882737 | biostudies-other

Photochemical Asymmetric Nickel-Catalyzed Acyl Cross-Coupling.

Project description:Photochemical enantioselective nickel-catalyzed cross-coupling reactions are difficult to implement. We report a visible-light-mediated strategy that successfully couples symmetrical anhydrides and 4-alkyl dihydropyridines (DHPs) to afford enantioenriched ?-substituted ketones under mild conditions. The chemistry does not require exogenous photocatalysts. It is triggered by the direct excitation of DHPs, which act as a radical source and as a reductant, facilitating the turnover of the chiral catalytic nickel complex.

| S-EPMC6900114 | biostudies-literature

Nickel-catalyzed migratory alkyl-alkyl cross-coupling reaction.

Project description:The selective cross-coupling of activated electrophiles with unactivated ones has been regarded as a challenging task in cross-electrophile couplings. Herein we describe a migratory cross-coupling strategy, which can overcome this obstacle to access the desired cross-coupling products. Accordingly, a selective migratory cross-coupling of two alkyl electrophiles has been accomplished by nickel catalysis. Remarkably, this alkyl-alkyl cross-coupling reaction provides a platform to prepare 2°-2° carbon-carbon bonds from 1° and 2° carbon coupling partners. Preliminary mechanistic studies suggest that chain-walking occurs at both alkyl halides in this reaction, thus a catalytic cycle with the key step involving two alkylnickel(ii) species is proposed for this transformation.

| S-EPMC8162388 | biostudies-literature

Coupling Photoresponsive Transmembrane Ion Transport with Transition Metal Catalysis.

Project description:Artificial ion transporters have been explored both as tools for studying fundamental ion transport processes and as potential therapeutics for cancer and channelopathies. Here we demonstrate that synthetic transporters may also be used to regulate the transport of catalytic metal ions across lipid membranes and thus control chemical reactivity inside lipid-bound compartments. We show that acyclic lipophilic pyridyltriazoles enable Pd(II) cations to be transported from the external aqueous phase across the lipid bilayer and into the interior of large unilamellar vesicles. In situ reduction generates Pd(0) species, which catalyze the generation of a fluorescent product. Photocaging the Pd(II) transporter allows for photoactivation of the transport process and hence photocontrol over the internal catalysis process. This work demonstrates that artificial transporters enable control over catalysis inside artificial cell-like systems, which could form the basis of biocompatible nanoreactors for applications such as drug synthesis and delivery or to mediate phototargeted catalyst delivery into cells.

| S-EPMC10885138 | biostudies-literature

Decarbonylative organoboron cross-coupling of esters by nickel catalysis.

Project description:The Suzuki-Miyaura cross-coupling is a metal-catalysed reaction in which boron-based nucleophiles and halide-based electrophiles are reacted to form a single molecule. This is one of the most reliable tools in synthetic chemistry, and is extensively used in the synthesis of pharmaceuticals, agrochemicals and organic materials. Herein, we report a significant advance in the choice of electrophilic coupling partner in this reaction. With a user-friendly and inexpensive nickel catalyst, a range of phenyl esters of aromatic, heteroaromatic and aliphatic carboxylic acids react with boronic acids in a decarbonylative manner. Overall, phenyl ester moieties function as leaving groups. Theoretical calculations uncovered key mechanistic features of this unusual decarbonylative coupling. Since extraordinary numbers of ester-containing molecules are available both commercially and synthetically, this new 'ester' cross-coupling should find significant use in synthetic chemistry as an alternative to the standard halide-based Suzuki-Miyaura coupling.

| S-EPMC4491840 | biostudies-other

Cascade Cross-Coupling of Dienes: Photoredox and Nickel Dual Catalysis.

Project description:Chemical transformations based on cascade reactions have the potential to simplify the preparation of diverse and architecturally complex molecules dramatically. Herein, we disclose an unprecedented and efficient method for the cross-coupling of radical precursors, dienes, and electrophilic coupling partners via a photoredox- and nickel-enabled cascade cross-coupling process. The cascade reaction furnishes a diverse array of saturated carbo- and heterocyclic scaffolds, thus providing access to a quick gain in C-C bond saturation.

| S-EPMC6973272 | biostudies-literature

Nickel-Catalyzed Stille Cross Coupling of C-O Electrophiles.

Project description:Aryl sulfamates, tosylates, and mesylates undergo efficient Ni-catalyzed cross coupling with diverse organostannanes in the presence of relatively unhindered alkylphosphine ligands and KF. The coupling is valuable for difficult bond constructions, such as aryl- heteroaryl, aryl-alkenyl, and aryl-alkynyl, using non-triflate phenol derivatives. A combination of experimental and computational studies implicate an unusual mechanism for transmetalation involving an 8-centered cyclic transition state. This reaction is inhibited by chloride sources due to slow transmetalation of organostannanes at a Ni(II)-chloride intermediate. These studies help to explain why prior efforts to achieve Ni-catalyzed Stille coupling of phenol derivatives were unsuccessful.

| S-EPMC6497415 | biostudies-literature

Integrating Allyl Electrophiles into Nickel-Catalyzed Conjunctive Cross-Coupling.

Project description:Allylation and conjunctive cross-coupling represent two useful, yet largely distinct, reactivity paradigms in catalysis. The union of these two processes would offer exciting possibilities in organic synthesis but remains largely unknown. Herein, we report the use of allyl electrophiles in nickel-catalyzed conjunctive cross-coupling with a non-conjugated alkene and dimethylzinc. The transformation is enabled by weakly coordinating, monodentate aza-heterocycle directing groups that are useful building blocks in synthesis, including saccharin, pyridones, pyrazoles, and triazoles. The reaction occurs under mild conditions and is compatible with a wide range of allyl electrophiles. High chemoselectivity through substrate directivity is demonstrated by the facile reactivity of the β-γ alkene of the starting material, whereas the ϵ-ζ alkene of the product is preserved. The generality of this approach is further illustrated through the development of an analogous method with alkyne substrates. Mechanistic studies reveal the importance of the dissociation of the weakly coordinating directing group to allow the allyl moiety to bind and facilitate C(sp3 )-C(sp3 ) reductive elimination.

| S-EPMC7184930 | biostudies-literature

Nickel-Catalyzed Kumada Cross-Coupling Reactions of Benzylic Sulfonamides.

Project description:Herein, we report a Kumada cross-coupling reaction of benzylic sulfonamides. The scope of the transformation includes acyclic and cyclic sulfonamide precursors that cleanly produce highly substituted acyclic fragments. Preliminary data are consistent with a stereospecific mechanism that allows for a diastereoselective reaction.

| S-EPMC8512530 | biostudies-literature

Enantioselective, nickel-catalyzed Suzuki cross-coupling of quinolinium ions.

Project description:Quinolinium ions are engaged in an asymmetric, Ni-catalyzed Suzuki cross-coupling to yield 2-aryl- and 2-heteroaryl-1,2-dihydroquinolines. Key to the development of this method is the use of a Ni(II) precatalyst that activates without the need for strong reductants or high temperatures. The Ni-iminium activation mode is demonstrated as an exceptionally mild pathway to generate enantioenriched products from racemic starting materials.

| S-EPMC3924560 | 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