Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Radical-anion coupling through reagent design: hydroxylation of aryl halides.

ABSTRACT: The design and development of an oxime-based hydroxylation reagent, which can chemoselectively convert aryl halides (X = F, Cl, Br, I) into phenols under operationally simple, transition-metal-free conditions is described. Key to the success of this approach was the identification of a reducing oxime anion which can interact and couple with open-shell aryl radicals. Experimental and computational studies support the proposed radical-nucleophilic substitution chain mechanism.

SUBMITTER: Greener AJ

PROVIDER: S-EPMC8580057 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Radical-anion coupling through reagent design: hydroxylation of aryl halides.

Greener Andrew J AJ Ubysz Patrycja P Owens-Ward Will W Smith George G Ocaña Ivan I Whitwood Adrian C AC Chechik Victor V James Michael J MJ

Chemical science 20211022 43

The design and development of an oxime-based hydroxylation reagent, which can chemoselectively convert aryl halides (X = F, Cl, Br, I) into phenols under operationally simple, transition-metal-free conditions is described. Key to the success of this approach was the identification of a reducing oxime anion which can interact and couple with open-shell aryl radicals. Experimental and computational studies support the proposed radical-nucleophilic substitution chain mechanism. ...[more]

PMID: 34881017

Similar Datasets

Cobalt-Catalyzed Suzuki Biaryl Coupling of Aryl Halides.

Project description:Readily accessed cobalt pre-catalysts with N-heterocyclic carbene ligands catalyze the Suzuki cross-coupling of aryl chlorides and bromides with alkyllithium-activated arylboronic pinacolate esters. Preliminary mechanistic studies indicate that the cobalt species is reduced to Co0 during the reaction.

| S-EPMC5767760 | biostudies-literature

Enantioselective cross-coupling of meso-epoxides with aryl halides.

Project description:The first enantioselective cross-electrophile coupling of aryl bromides with meso-epoxides to form trans-?-arylcycloalkanols is presented. The reaction is catalyzed by a combination of (bpy)NiCl2 and a chiral titanocene under reducing conditions. Yields range from 57 to 99% with 78-95% enantiomeric excess. The 30 examples include a variety of functional groups (ether, ester, ketone, nitrile, ketal, trifluoromethyl, sulfonamide, sulfonate ester), both aryl and vinyl halides, and five- to seven-membered rings. The intermediacy of a carbon radical is strongly suggested by the conversion of cyclooctene monoxide to an aryl [3.3.0]bicyclooctanol.

| S-EPMC4415026 | biostudies-literature

Nickel-Catalyzed Electroreductive Coupling of Alkylpyridinium Salts and Aryl Halides.

Project description:An electrochemical, nickel-catalyzed reductive coupling of alkylpyridinium salts and aryl halides is reported. High-throughput experimentation (HTE) was employed for rapid reaction optimization and evaluation of a broad scope of pharmaceutically relevant structurally diverse aryl halides, including complex drug-like substrates. In addition, the transformation is compatible with both primary and secondary alkylpyridinium salts with distinct conditions. Mechanistic insights were critical to enhance the efficiency of coupling using secondary alkylpyridinium salts. Systematic comparisons of the electrochemical and non-electrochemical methods revealed the complementary scope and efficiency of the two approaches.

| S-EPMC10769313 | biostudies-literature

Mechanism and selectivity in nickel-catalyzed cross-electrophile coupling of aryl halides with alkyl halides.

Project description:The direct cross-coupling of two different electrophiles, such as an aryl halide with an alkyl halide, offers many advantages over conventional cross-coupling methods that require a carbon nucleophile. Despite its promise as a versatile synthetic strategy, a limited understanding of the mechanism and origin of cross selectivity has hindered progress in reaction development and design. Herein, we shed light on the mechanism for the nickel-catalyzed cross-electrophile coupling of aryl halides with alkyl halides and demonstrate that the selectivity arises from an unusual catalytic cycle that combines both polar and radical steps to form the new C-C bond.

| S-EPMC3946589 | biostudies-literature

Negishi coupling of secondary alkylzinc halides with aryl bromides and chlorides.

Project description:An efficient palladium-catalyzed process has been developed for Negishi coupling of secondary alkylzinc halides with a wide range of aryl bromides and activated aryl chlorides. A palladium catalyst composed of a new biaryldialkylphosphine ligand, CPhos, effectively promotes the rate of the reductive elimination step relative to the rate of the undesired beta-hydride elimination. The broad substrate scope and excellent ratio of the desired secondary to the undesired primary coupling product make this method a powerful and reliable tool for C(sp(3))-C(sp(2)) bond formation.

| S-EPMC2746668 | biostudies-literature

Preparation of potassium azidoaryltrifluoroborates and their cross-coupling with aryl halides.

Project description:Potassium azidoaryltrifluoroborates have been prepared from the corresponding haloaryltrifluoroborates in 73-98% yields. Also, we successfully cross-coupled the azido-functionalized organotrifluoroborates and carried out a one-pot sequential cross-coupling/1,3-dipolar cycloaddition and a one-pot cross-coupling/azide reduction process.

| S-EPMC2751812 | biostudies-literature

Total synthesis of pareitropone via radical anion coupling.

Project description:A concise (9-step) synthesis of the tropoloisoquinoline alkaloid pareitropone has been achieved starting from 2-bromoisovanillin. The key step features oxidative cyclization of a readily available phenolic nitronate for the convenient construction of the fused tropone ring. This work underscores the synthetic utility of intramolecular oxidative coupling reactions of phenolic nitronates.

| S-EPMC2929295 | biostudies-literature

Nickel-Catalyzed Cross-Coupling of Aryl Halides with Alkyl Halides: Ethyl 4-(4-(4-methylphenylsulfonamido)-phenyl)butanoate.

Project description: Not available

| S-EPMC4012698 | biostudies-literature

Palladium-catalyzed hydroxylation of aryl and heteroaryl halides enabled by the use of a palladacycle precatalyst.

Project description:A method for the hydroxylation of aryl and heteroaryl halides, promoted by a catalyst based on a biarylphosphine ligand tBuBrettPhos (L5) and its corresponding palladium precatalyst (1), is described. The reactions allow the cross-coupling of both potassium and cesium hydroxides with (hetero)aryl halides to afford a variety of phenols and hydroxylated heteroarenes in high to excellent yield.

| S-EPMC4049244 | biostudies-literature

Cobalt-Catalyzed Cross-Coupling of Functionalized Alkylzinc Reagents with (Hetero)Aryl Halides.

Project description:A combination of 10?% CoCl2 and 20?% 2,2'-bipyridine ligands enables cross-coupling of functionalized primary and secondary alkylzinc reagents with various (hetero)aryl halides. Couplings with 1,3- and 1,4-substituted cycloalkylzinc reagents proceeded diastereoselectively leading to functionalized heterocycles with high diastereoselectivities of up to 98:2. Furthermore, alkynyl bromides react with primary and secondary alkylzinc reagents providing the alkylated alkynes.

| S-EPMC7154687 | 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