Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Anaerobic photoinduced Cu(0/I)-mediated Glaser coupling in a radical pathway.

ABSTRACT: The reaction mechanism of the historic copper-catalyzed Glaser coupling has been debated to be based on redox cycles of Cu ions in specific oxidation states or on a radical mechanism based on Cu(0)/Cu(I). Here, the authors demonstrate two coexisting Glaser coupling pathways which can be differentiated by anaerobic/irradiation or aerobic reaction conditions. Without O₂, copper(I) acetylides undergo a photo-excited pathway to generate highly reactive alkynyl radicals, which combine together to form a homo-coupling product or individually react with diverse X-H (X = C, N, O, S and P) substrates via hydrogen atom transfer. With O₂, copper(I) acetylides are oxidized to become a Cu-acetylide/Cu-O merged Cu(I/II) intermediate for further oxidative coupling. This work not only complements the radical mechanism for Glaser coupling, but also provides a mild way to access highly energetic alkynyl radicals for efficient organic transformations.

SUBMITTER: Zhang S

PROVIDER: S-EPMC10598264 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Anaerobic photoinduced Cu(0/I)-mediated Glaser coupling in a radical pathway.

Zhang Siqi S Zhao Liang L

Nature communications 20231024 1

The reaction mechanism of the historic copper-catalyzed Glaser coupling has been debated to be based on redox cycles of Cu ions in specific oxidation states or on a radical mechanism based on Cu(0)/Cu(I). Here, the authors demonstrate two coexisting Glaser coupling pathways which can be differentiated by anaerobic/irradiation or aerobic reaction conditions. Without O<sub>2</sub>, copper(I) acetylides undergo a photo-excited pathway to generate highly reactive alkynyl radicals, which combine toge ...[more]

PMID: 37875487

Similar Datasets

Strong Anionic/Charge-Neutral Block Copolymers from Cu(0)-Mediated Reversible Deactivation Radical Polymerization.

Project description:Despite recent developments in controlled polymerization techniques, the straightforward synthesis of block copolymers that feature both strong anionic and charge-neutral segments remains a difficult endeavor. In particular, solubility issues may arise during the direct synthesis of strong amphiphiles and typical postpolymerization deprotection often requires harsh conditions. To overcome these challenges, we employed Cu(0)-mediated reversible deactivation radical polymerization (Cu(0)-RDRP) on a hydrophobic isobutoxy-protected 3-sulfopropyl acrylate. Cu(0)-RDRP enables the rapid synthesis of the polymer, reaching high conversions and low dispersities while using a single solvent system and low amounts of copper species. These macromolecules are straightforward to characterize and can subsequently be deprotected in a mild yet highly efficient fashion to expose their strongly charged nature. Furthermore, a protected sulfonate segment could be grown from a variety of charge-neutral macroinitiators to produce, after the use of the same deprotection chemistry, a library of amphiphilic, double-hydrophilic as well as thermoresponsive block copolymers (BCPs). The ability of these various BCPs to self-assemble in aqueous media was further studied by dynamic light scattering, ζ-potential measurements as well as atomic force and electron microscopy.

| S-EPMC9558488 | biostudies-literature

Benzotriazole as an Efficient Ligand in Cu-Catalyzed Glaser Reaction.

Project description:Benzotriazole has been established as an efficient ligand in Cu-catalyzed cross-coupling of terminal alkynes to form 1,3-dialkynes using CuI as the catalyst and K2CO3 as the base at room temperature in an open round-bottom flask. The established protocol has the following notable advantages: simple to handle, easy work-up, mild reaction condition, high substrate scope, requirement of less quantity of ligand and also Cu-catalyst, less expensive, and high reaction yield.

| S-EPMC6648008 | biostudies-literature

A merged copper(I/II) cluster isolated from Glaser coupling.

Project description:Ubiquitous copper-oxygen species are pivotal in enabling multifarious oxidation reactions in biological and chemical transformations. We herein construct a macrocycle-protected mixed-valence cluster [(tBuC≡CCuI3)-(μ2-OH)-CuII] by merging a copper acetylide cluster with a copper-oxygen moiety formed in Glaser coupling. This merged Cu(I/II) cluster shows remarkably strong oxidation capacity, whose reduction potential is among the most positive for Cu(II) and even comparable with some Cu(III) species. Consequently, the cluster exhibits high hydrogen atom transfer (HAT) reactivity with inert hydrocarbons. In contrast, the degraded [CuII-(μ2-OH)-CuII] embedded in a small macrocyclic homologue shows no HAT reactivity. Theoretical calculations indicate that the strong oxidation ability of Cu(II) in [(tBuC≡CCuI3)-(μ2-OH)-CuII] is mainly ascribed to the uneven charge distribution of Cu(I) ions in the tBuC≡CCuI3 unit because of significant [dCu(I) → π*(C≡C)] back donation. The present study on in situ formed metal clusters opens a broad prospect for mechanistic studies of Cu-based catalytic reactions.

| S-EPMC6813345 | biostudies-literature

Tuning the Reactivity of Radical through a Triplet Diradical Cu(II) Intermediate in Radical Oxidative Cross-Coupling.

Project description:Highly selective radical/radical cross-coupling is paid more attention in bond formations. However, due to their intrinsic active properties, radical species are apt to achieve homo-coupling instead of cross-coupling, which makes the selective cross-coupling as a great challenge and almost untouched. Herein a notable strategy to accomplish direct radical/radical oxidative cross-coupling has been demonstrated, that is metal tuning a transient radical to a persistent radical intermediate followed by coupling with another transient radical. Here, a transient nitrogen-centered radical is tuned to a persistent radical complex by copper catalyst, followed by coupling with a transient allylic carbon-centered radical. Firstly, nitrogen-centered radical generated from N-methoxybenzamide stabilized by copper catalyst was successfully observed by EPR. Then DFT calculations revealed that a triplet diradical Cu(II) complex formed from the chelation N-methoxybenzamide nitrogen-centered radical to Cu(II) is a persistent radical species. Moreover, conceivable nitrogen-centered radical Cu(II) complex was observed by high-resolution electrospray ionization mass spectrometry (ESI-MS). Ultimately, various allylic amides derivatives were obtained in good yields by adopting this strategy, which might inspire a novel and promising landscape in radical chemistry.

| S-EPMC4630646 | biostudies-literature

A Cu-Catalysed Radical Cross-Dehydrogenative Coupling Approach to Acridanes and Related Heterocycles.

Project description:The synthesis of acridanes and related compounds through a Cu-catalysed radical cross-dehydrogenative coupling of simple 2-[2-(arylamino)aryl]malonates is reported. This method can be further streamlined to a one-pot protocol involving the in situ fomation of the 2-[2-(arylamino)aryl]malonate by α-arylation of diethyl malonate with 2-bromodiarylamines under Pd catalysis, followed by Cu-catalysed cyclisation.

| S-EPMC5396374 | biostudies-literature

Supported Cu<sup>0</sup> nanoparticles catalyst for controlled radical polymerization reaction and block-copolymer synthesis.

Project description:The synthesis of Cu0 nanoparticles on different supports and their activity in controlled living radical polymerization processes is presented. The type of support influences the final size of the copper nanoparticles as well as their adhesion to the support. These aspects have a direct influence on the characteristics of the polymers obtained. The best results were obtained for SiO2 particles, which afforded a good molecular weight distribution (Mw/Mn = 1.25). The activity, recovery and recycling of the catalyst was explored for ultrafast polymerization reaction of butyl acrylate. Further, the terminal bromine reactivity was used for the synthesis of a block poly(n butyl acrylate-block-styrene). The influence of ligand type on the control of the reaction was studied. Also, a straightforward polymerization procedure without any ligand afforded a polydispersity value of 1.38.

| S-EPMC5583343 | biostudies-literature

On the Mechanism of Pd(0)-Catalyzed, Cu(I) Carboxylate-Mediated Thioorganic-Boronic Acid Desulfitative Coupling. A Non-innocent Role for Carboxylate Ligand.

Project description:Computational studies of the mechanism of the Pd-catalyzed, Cu(I)-carboxylate-mediated desulfitative coupling of thioorganics with boronic acids have determined that the requisite Cu(I)-carboxylate plays multiple important roles. The Cu(I)-carboxylate enhances both the transmetalation and the C-C reductive elimination steps: it acts as a reactive transmetalation center and it provides a vital carboxylate ligand. The carboxylate ligand functions not only as an activator for the boronic acid, but it also displaces a phosphine ligand at the palladium center generating a catalytically competent mono-phosphine-palladium intermediate.

| S-EPMC2742425 | biostudies-literature

Photoinduced inverse Sonogashira coupling reaction.

Project description:Alkynes are widely used in chemistry, medicine and materials science. Here we demonstrate a transition-metal and photocatalyst-free inverse Sonogashira coupling reaction between iodoalkynes and (hetero)arenes or alkenes under visible-light irradiation. Mechanistic and computational studies suggest that iodoalkynes can be directly activated by visible light irradiation, and an excited state iodoalkyne acted as an "alkynyl radical synthetic equivalent", reacting with a series of C(sp2)-H bonds for coupling products. This work should open new windows in radical chemistry and alkynylation method.

| S-EPMC9241966 | biostudies-literature

Reductive Cross-Coupling of Olefins via a Radical Pathway.

Project description:Olefins are widely available at low costs, which explains the usefulness of developing new methods for their functionalization. Here we report a simple protocol that uses a photoredox catalyst and an inexpensive thiol catalyst to stitch together two olefins, forming a new C-C bond. Specifically, an electron-poor olefin is reduced by the photoredox catalyst to generate, upon protonation, a carbon radical, which is then captured by a neutral olefin. This intermolecular cross-coupling process provides a tool for rapidly synthesizing sp3-dense molecules from olefins using an unconventional disconnection.

| S-EPMC10682986 | biostudies-literature

Photoinduced Intermolecular Radical Hydroalkylation of Olefins via Ligated Boryl Radicals-Mediated Halogen Atom Transfer.

Project description:Light-mediated Halogen-Atom Transfer (XAT) has become a significant methodology in contemporary synthesis. Unlike α-aminoalkyl and silyl radicals, ligated boryl radicals (LBRs) have not been extensively explored as halogen atom abstractors. In this study, we introduce NHC-ligated boranes as optimal radical chain carriers for the intermolecular reductive radical hydroalkylation and hydroarylation of electron-deficient olefins by using direct UV-A light irradiation. DFT analysis allowed us to rationalize the critical role of the NHC ligand in facilitating efficient chain propagation.

| S-EPMC11250028 | 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