Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

C-C bond formation via double C-H functionalization: aerobic oxidative coupling as a method for synthesizing heterocoupled biaryls.

ABSTRACT: The aerobic oxidative coupling of arenes such as benzofuran and N-substituted indoles with benzene and derivatives thereof is described. The reaction is shown to take place in both inter- and intramolecular scenarios.

SUBMITTER: Dwight TA

PROVIDER: S-EPMC2566853 | biostudies-literature | 2007 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

C-C bond formation via double C-H functionalization: aerobic oxidative coupling as a method for synthesizing heterocoupled biaryls.

Dwight Timothy A TA Rue Nicholas R NR Charyk Dagmara D Josselyn Ryan R DeBoef Brenton B

Organic letters 20070707 16

The aerobic oxidative coupling of arenes such as benzofuran and N-substituted indoles with benzene and derivatives thereof is described. The reaction is shown to take place in both inter- and intramolecular scenarios. ...[more]

PMID: 17616203

Similar Datasets

A new paradigm for carbon-carbon bond formation: aerobic, copper-templated cross-coupling.

Project description:Thiol esters and boronic acids react to produce ketones under aerobic conditions in the presence of catalytic quantities of a CuI or CuII salt. The reaction occurs at reasonable rates between room temperature and 50 degrees C at neutral pH using thiol esters derived from bulky 2 degrees amides of thiosalicylamides such as those based on N-tert-butyl-2-mercaptobenzamide. In this mechanistically unprecedented reaction system, the carbon-carbon bond formation occurs through templating of the thiol ester and the boronic acid at copper; the system is rendered catalytic in copper under the aerobic conditions.

| S-EPMC2561227 | biostudies-literature

Metal-free intermolecular oxidative C-N bond formation via tandem C-H and N-H bond functionalization.

Project description:The development of a novel intermolecular oxidative amination reaction, a synthetic transformation that involves the simultaneous functionalization of both a N-H and C-H bond, is described. The process, which is mediated by an I(III) oxidant and contains no metal catalysts, provides a rapid and green method for synthesizing protected anilines from simple arenes and phthalimide. Mechanistic investigations indicate that the reaction proceeds via nucleophilic attack of the phthalimide on an aromatic radical cation, as opposed to the electrophilic aromatic amination that has been reported for other I(III) amination reactions. The application of this new reaction to the synthesis of a variety of substituted aniline derivatives is demonstrated.

| S-EPMC3233640 | biostudies-literature

Transition-Metal-Free Oxidative Cross-Coupling of Tetraarylborates to Biaryls Using Organic Oxidants.

Project description:Readily prepared tetraarylborates undergo selective (cross)-coupling through oxidation with Bobbitt's salt to give symmetric and unsymmetric biaryls. The organic oxoammonium salt can be used either as a stoichiometric oxidant or as a catalyst in combination with in situ generated NO2 and molecular oxygen as the terminal oxidant. For selected cases, oxidative coupling is also possible with NO2 /O2 without any additional nitroxide-based cocatalyst. Transition-metal-free catalytic oxidative ligand cross-coupling of tetraarylborates is unprecedented and the introduced method provides access to various biaryl and heterobiaryl systems.

| S-EPMC7496537 | biostudies-literature

Oxidative palladium(II) catalysis: A highly efficient and chemoselective cross-coupling method for carbon-carbon bond formation under base-free and nitrogenous-ligand conditions.

Project description:We report herein the development of a general and mild protocol of oxygen-promoted Pd(II) catalysis resulting in the selective cross-couplings of alkenyl- and arylboron compounds with various olefins. Unlike most cross-coupling reactions, this new methodology works well even in the absence of bases, consequently averting undesired homo-couplings. Nitrogen-based ligands including dimethyl-phenanathroline enhance reactivities and offer a highly efficient and stereoselective methodology to overcome challenging substrate limitations. For instance, oxidative palladium(II) catalysis is effective with highly substituted alkenes and cyclic alkenes, which are known to be incompatible with other known catalytic conditions. Most examined reactions progressed smoothly to completion at low temperatures and in short times. These interesting results provide mechanistic insights and utilities for a new paradigm of palladium catalytic cycles without bases.

| S-EPMC2602842 | biostudies-literature

Aerobic Oxidative Coupling of o-Xylene: Discovery of 2-Fluoropyridine as a Ligand to Support Selective Pd-Catalyzed C-H Functionalization.

Project description:An improved method for direct oxidative coupling of o-xylene could provide streamlined access to an important monomer used in polyimide resins. The use of 2-fluoropyridine as a ligand has been found to enable unprecedented levels of chemo- and regioselectivity in this Pd-catalyzed aerobic oxidative coupling reaction. Preliminary insights have been obtained into the origin of the effectiveness of 2-fluoropyridine as a ligand.

| S-EPMC3049937 | biostudies-literature

Palladium-catalyzed method for the synthesis of carbazoles via tandem C-H functionalization and C-N bond formation.

Project description:The development of a new method for the assembly of unsymmetrical carbazoles is reported. The strategy involves the selective intramolecular functionalization of an arene C-H bond and the formation of a new arene C-N bond. The substitution pattern of the carbazole product can be controlled by the design of the biaryl amide substrate, and the method is compatible with a variety of functional groups. The utility of the new protocol was demonstrated by the concise synthesis of three natural products from commercially available materials.

| S-EPMC2748774 | biostudies-literature

Connecting remote C-H bond functionalization and decarboxylative coupling using simple amines.

Project description:Transition metal-catalysed C-H functionalization and decarboxylative coupling are two of the most notable synthetic strategies developed in the past 30 years. Here, we connect these two reaction pathways using bases and a simple Pd-based catalyst system to promote a para-selective C-H functionalization reaction from benzylic electrophiles. Experimental and computational mechanistic studies suggest a pathway that involves an uncommon Pd-catalysed dearomatization of the benzyl moiety followed by a base-enabled rearomatization through a formal 1,5-hydrogen migration. This reaction complements 'C-H activation' strategies that convert inert C-H bonds into C-metal bonds prior to C-C bond formation. Instead, this reaction exploits an inverted sequence and promotes C-C bond formation prior to deprotonation. These studies provide an opportunity to develop general para-selective C-H functionalization reactions from benzylic electrophiles and show how new reactive modalities may be accessed with careful control of the reaction conditions.

| S-EPMC7192790 | biostudies-literature

Double heteroatom functionalization of arenes using benzyne three-component coupling.

Project description:Arynes participate in three-component coupling reactions with N, S, P, and Se functionalities to yield 1,2-heteroatom-difunctionalized arenes. Using 2-iodophenyl arylsulfonates as benzyne precursors, we could effectively add magnesiated S-, Se-, and N-nucleophilic components to the strained triple bond. In the same pot, addition of electrophilic N, S, or P reagents and a copper(I) catalyst trapped the intermediate aryl Grignard to produce a variety of 1,2-difunctionalized arenes.

| S-EPMC4832838 | biostudies-other

Synthesis of sulfur-containing heterocycles through oxidative carbon-hydrogen bond functionalization.

Project description:Vinyl sulfides react rapidly and efficiently with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to form ?,?-unsaturated thiocarbenium ions through oxidative carbon-hydrogen bond cleavage. These electrophiles couple with appended ?-nucleophiles to yield sulfur-containing heterocycles through carbon-carbon bond formation. Several nucleophiles are compatible with the procedure, and the reactions generally proceed through readily predictable transition states.

| S-EPMC3321134 | biostudies-literature

Bimodal supramolecular functionalization of carbon nanotubes triggered by covalent bond formation.

Project description:Many applications of carbon nanotubes require their chemical functionalization. Both covalent and supramolecular approaches have been extensively investigated. A less trodden path is the combination of both covalent and noncovalent chemistries, where the formation of covalent bonds triggers a particularly stable noncovalent interaction with the nanotubes. We describe a series of naphthalene diimide (NDI) bisalkene molecules that, upon mixing with single-walled carbon nanotubes (SWNTs) and Grubbs' catalyst, undergo two different reaction pathways. On one hand, they ring-close around the SWNTs to form rotaxane-like mechanically interlocked derivatives of SWNTs (MINTs). Alternatively, they oligomerize and then wrap around the SWNTs. The balance of MINTs to oligomer-wrapped SWNTs depends on the affinity of the NDI molecules for the SWNTs and the kinetics of the metathesis reactions, which can be controlled by varying the solvent. Thorough characterization of the products (TGA, TEM, AFM, Raman, UV-vis-NIR, PLE, XPS and UPS) confirms their structure and shows that each type of functionalization affects the electronic properties of the SWNTs differently.

| S-EPMC5364655 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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