Aerobic copper-catalyzed organic reactions.

  title={Aerobic copper-catalyzed organic reactions.},
  author={Scott E. Allen and Ryan R. Walvoord and Rosaura Padilla-Salinas and Marisa C. Kozlowski},
  journal={Chemical reviews},
  volume={113 8},
The chemistry of copper is extremely rich because it can easily access Cu0, CuI, CuII, and CuIII oxidation states allowing it to act through one-electron or two-electron processes. As a result, both radical pathways and powerful two-electron bond forming pathways via organmetallic intermediates, similar to those of palladium, can occur. In addition, the different oxidation states of copper associate well with a large number of different functional groups via Lewis acid interactions or… 
Copper-Promoted Functionalization of Organic Molecules: from Biologically Relevant Cu/O2 Model Systems to Organometallic Transformations.
The most relevant research in which copper promotes or catalyzes the functionalization of organic molecules, including biological catalysis, bioinspired model systems, and organometallic reactivity is summarized.
Reoxidation of Transition‐metal Catalysts with O2
Transition-metal catalyzed oxidation reactions are central components of organic chemistry. On behalf of green and sustainable chemistry, molecular oxygen (O2) has been considered as an ideal oxidant
Mediator-Enabled Electrocatalysis with Ligandless Copper for Anaerobic Chan-Lam Coupling Reactions.
The implementation of substoichiometric quantities of redox mediators to address limitations to Cu-catalyzed electrosynthesis in Chan-Lam coupling of aryl-, heteroaryl-, and alkylamines with aryLboronic acids in the absence of chemical oxidants is reported.
An isocyanide ligand for the rapid quenching and efficient removal of copper residues after Cu/TEMPO-catalyzed aerobic alcohol oxidation and atom transfer radical polymerization
Transition metal catalysts play a prominent role in modern organic and polymer chemistry, enabling many transformations of academic and industrial significance. However, the use of organometallic
Intermediacy of Copper(I) under Oxidative Conditions in the Aerobic Copper-Catalyzed Decarboxylative Thiolation of Benzoic Acids
Despite the growing importance of oxidative decarboxylative coupling (ODC) reactions, they often require silver salts to serve as both oxidant and decarboxylation mediator. The use of O2 in place of
Cu(III)-Mediated Aerobic Oxidations
CuIII species have been invoked in many copper-catalyzed transformations including cross-coupling reactions and oxidation reactions. In this review, we will discuss seminal discoveries that have
Mechanistic Study on Cu(II)-Catalyzed Oxidative Cross-Coupling Reaction between Arenes and Boronic Acids under Aerobic Conditions.
An in-depth experimental and computational study on the mechanism of a Cu(II)-catalyzed oxidative cross-coupling reaction between arenes and boronic acids with air as the oxidant is reported.
Halide-promoted dioxygenolysis of a carbon-carbon bond by a copper(II) diketonate complex.
The results of this study suggest that anion coordination can play a significant role in influencing Copper(II) halide-catalyzed reactions in which diketonates are oxidatively cleaved using O2 as the terminal oxidant.
Reactions Catalysed by a Binuclear Copper Complex: Aerobic Cross Dehydrogenative Coupling of N-Aryl Tetrahydroisoquinolines.
Since it is more efficient than and mechanistically distinct from the well-studied simple copper salts such as CuBr and CuCl2 , the binuclear copper catalyst provides a new tool for oxidative coupling reactions.


Copper-catalyzed aerobic oxidative C-H functionalizations: trends and mechanistic insights.
This work has reported several recently reported Cu-catalyzed C-H oxidation reactions that feature substrates that are electron-deficient or appear unlikely to undergo single-electron transfer to copper(II), and evidence has been obtained for the involvement of organocopper(III) intermediates in the reaction mechanism.
Homogeneous Copper-Catalyzed Oxidations
The bioinorganic chemistry of copper has provided a stimulating background for exciting research on homogeneous copper-catalyzed reactions in recent years, and this review starts with a brief and
Selective Catalytic Oxidation of CH Bonds with Molecular Oxygen
Although catalytic reductions, cross‐couplings, metathesis, and oxidation of CC double bonds are well established, the corresponding catalytic hydroxylations of CH bonds in alkanes, arenes, or
Oxidant types in copper–dioxygen chemistry: the ligand coordination defines the Cun-O2 structure and subsequent reactivity
The considerable recent advances in copper–dioxygen coordination chemistry demonstrate the existence of a variety of dioxygen-derived Cun-O2 complexes, forming a basis for discussion of alternate
Ligand dependence in the copper-catalyzed oxidation of hydroquinones.
Biomimetic metal-radical reactivity: aerial oxidation of alcohols, amines, aminophenols and catechols catalyzed by transition metal complexes
The presence of a primary kinetic isotope effect, similar to that for galactose oxidase, provides compelling evidence that H-atom abstraction from the α-C-atom of the substrates is the rate-limiting step.
Catalytic sulfoxidation by dinuclear copper complexes.
It is reported that m-h 2 :h 2 -peroxodicopper(II) complexes derived from diaminetetrabenzimidazole ligands can also support a sulfoxidation reaction with O2 and that with a suitable sacrificial co-substrate the reaction can be carried out catalytically, similarly to reactions promoted by tyrosinase.
Copper-catalyzed aerobic oxidative functionalization of an arene C-H bond: evidence for an aryl-copper(III) intermediate.
Kinetic and in situ spectroscopic studies demonstrate the involvement of three different oxidation states of Cu in the catalytic mechanism, including an aryl-Cu(III) intermediate, establishing a novel mechanistic pathway that has implications for numerous other Cu-catalyzed aerobic oxidation reactions.
Room Temperature Aerobic Copper–Catalysed Selective Oxidation of Primary Alcohols to Aldehydes
A novel and very mild method for the oxidation of primary alcohols to aldehydes with excellent conversions has been developed. The reaction is carried out under air at room temperature and is