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 π-coordination. In total, these feature confer a remarkably broad range of activities allowing copper to catalyze the oxidation and oxidative union of many substrates.

Oxygen is a highly atom economical, environmentally benign, and abundant oxidant, which makes it ideal in many ways.1 The high activation energies in the reactions of oxygen require that catalysts be employed.2 In combination with molecular oxygen, the chemistry of copper catalysis increases exponentially since oxygen can act as either a sink for electrons (oxidase activity) and/or as a source of oxygen atoms that are incorporated into the product (oxygenase activity). The oxidation of copper with oxygen is a facile process allowing catalytic turnover in net oxidative processes and ready access to the higher CuIII oxidation state, which enables a range of powerful transformations including two-electron reductive elimination to CuI. Molecular oxygen is also not hampered by toxic byproducts, being either reduced to water, occasionally via H2O2 (oxidase activity) or incorporated into the target structure with high atom economy (oxygenase activity). Such oxidations using oxygen or air (21% oxygen) have been employed safely in numerous commodity chemical continuous and batch processes.3

However, batch reactors employing volatile hydrocarbon solvents require that oxygen concentrations be kept low in the head space (typically <5–11%) to avoid flammable mixtures, which can limit the oxygen concentration in the reaction mixture.4,5,6 A number of alternate approaches have been developed allowing oxidation chemistry to be used safely across a broader array of conditions. For example, use of carbon dioxide instead of nitrogen as a diluent leads to reduced flammability.5 Alternately, water can be added to moderate the flammability allowing even pure oxygen to be employed.6 New reactor designs also allow pure oxygen to be used instead of diluted oxygen by maintaining gas bubbles in the solvent, which greatly improves reaction rates and prevents the build up of higher concentrations of oxygen in the head space.4a,7 Supercritical carbon dioxide has been found to be advantageous as a solvent due its chemical inertness towards oxidizing agents and its complete miscibility with oxygen or air over a wide range of temperatures.8 An number of flow technologies9 including flow reactors,10 capillary flow reactors,11 microchannel/microstructure structure reactors,12 and membrane reactors13 limit the amount of or afford separation of hydrocarbon/oxygen vapor phase thereby reducing the potential for explosions.

Enzymatic oxidizing systems based upon copper that exploit the many advantages and unique aspects of copper as a catalyst and oxygen as an oxidant as described in the preceding paragraphs are well known. They represent a powerful set of catalysts able to direct beautiful redox chemistry in a highly site-selective and stereoselective manner on simple as well as highly functionalized molecules. This ability has inspired organic chemists to discover small molecule catalysts that can emulate such processes. In addition, copper has been recognized as a powerful catalyst in several industrial processes (e.g. phenol polymerization, Glaser-Hay alkyne coupling) stimulating the study of the fundamental reaction steps and the organometallic copper intermediates. These studies have inspiried the development of nonenzymatic copper catalysts. For these reasons, the study of copper catalysis using molecular oxygen has undergone explosive growth, from 30 citations per year in the 1980s to over 300 citations per year in the 2000s.

A number of elegant reviews on the subject of catalytic copper oxidation chemistry have appeared. Most recently, reviews provide selected coverage of copper catalysts14 or a discussion of their use in the aerobic functionalization of C–H bonds.15 Other recent reviews cover copper and other metal catalysts with a range of oxidants, including oxygen, but several reaction types are not covered.16 Several other works provide a valuable overview of earlier efforts in the field.17 This review comprehensively covers copper catalyzed oxidation chemistry using oxygen as the oxidant up through 2011. Stoichiometric reactions with copper are discussed, as necessary, to put the development of the catalytic processes in context. Mixed metal systems utilizing copper, such as palladium catalyzed Wacker processes, are not included here. Decomposition reactions involving copper/oxygen and model systems of copper enzymes are not discussed exhaustively. To facilitate analysis of the reactions under discussion, the current mechanistic hypothesis is provided for each reaction. As our understanding of the basic chemical steps involving copper improve, it is expected that many of these mechanisms will evolve accordingly.

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Aerobic Copper-Catalyzed Organic Reactions

140 years ago Adolf von Baeyer proposed the structure of a heteroaromatic compound which revolutionized organic and medical chemistry: indole. After more than a century, indole itself and the complexity of naturally occurring indole derivatives continue to inspire and influence developments in synthetic chemistry. In particular, the ubiquitous presence of indole rings in pharmaceuticals, agrochemicals, and functional materials are testament to the ever increasing interest in the design of mild and efficient synthetic routes to functionalized indole derivatives. This Review emphasizes the achievements in the selective catalytic functionalization of indoles (C-C bond-forming processes) over the last four years.

Catalytic Functionalization of Indoles in a New Dimension

From 2000 to mid-2010: a fruitful decade for the synthesis of pyrazoles.

Free radical functionalization of organic compounds catalyzed by N-hydroxyphthalimide.

This review gives an overview of recent advances in the potential applications of superhydrophobic materials. Such properties are characterized by extremely high water contact angles and various adhesion properties. The conception of superhydrophobic materials has been possible by studying and mimicking natural surfaces. Now, various applications have emerged such as anti-icing, anti-corrosion and anti-bacterial coatings, microfluidic devices, textiles, oil–water separation, water desalination/purification, optical devices, sensors, batteries and catalysts. At least two parameters were found to be very important for many applications: the presence of air on superhydrophobic materials with self-cleaning properties (Cassie–Baxter state) and the robustness of the superhydrophobic properties (stability of the Cassie–Baxter state). This review will allow researchers to envisage new ideas and industrialists to advance in the commercialization of these materials.

Recent advances in the potential applications of bioinspired superhydrophobic materials

Selective Organocatalytic Oxygenation of Hydrocarbons by Dioxygen Using Anthraquinones and N-Hydroxyphthalimide

Cu2O was found to be a simple and efficient catalyst for the N-arylation of a variety of nitrogen-containing heterocycles with aryl and heteroaryl chlorides, bromides and iodides to give the products in excellent yields. The catalyst can be recovered simply and reused for several times without significant loss of activity.

Cu2O: a Simple and Efficient Reusable Catalyst for N-arylation of Nitrogen-containing Heterocycles with Aryl Halides

Highly dispersed cobalt-silicon mixed oxide [Co-SiO2] nanosphere was successfully prepared with a modified reverse-phase microemulsion method. This material was characterized in detail by X-ray diffraction, transmission electron microscopy, Fourier transform infrared, ultraviolet-visible diffuse reflectance spectra, X-ray absorption spectroscopy near-edge structure, and N2 adsorption-desorption measurements. High valence state cobalt could be easily obtained without calcination, which is fascinating for the catalytic application for its strong oxidation ability. In the selective oxidation of cyclohexane, Co-SiO2 acted as an efficient catalyst, and good activity could be obtained under mild conditions.

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Facile preparation of highly-dispersed cobalt-silicon mixed oxide nanosphere and its catalytic application in cyclohexane selective oxidation.

http://www.rsc.org/suppdata/CC/C0/C0CC03926H/C0CC03926H.PDF

Superhydrophobic materials as efficient catalysts for hydrocarbon selective oxidation.

According to the characteristics of the cyclohexane oxidation reaction a series of bifunctionalized hexagonal mesoporous silicas, CoPh-HMS, were designed and successfully synthesized by a one-step co-condensation route. The results of small-angle XRD, TEM, and N2 adsorption-desorption measurements showed that the resultant materials had well-ordered mesoscopic structures. Co 2+ ions were incorporated into the frameworks in tetrahedral coordination along with phenyl groups immobilized on the surface, confirmed by a careful spectroscopic (FT-IR, UV-visible, and 29 Si MAS NMR) study. The surfaces of the materials were proved to be more hydrophobic with higher Ph loading, and the largest water droplet contact angle is up to 110.50°. These materials were applied in the liquid-phase oxidation of cyclohexane with molecular oxygen as oxidant and tert-butyl hydroperoxide as initiator under solvent-free conditions. High activity could be obtained with these bifunctionalized catalysts being used. The modification effect of phenyl groups played an important role in the activity enhancement.

Qiaohong Zhang

Papers

Selective Organocatalytic Oxygenation of Hydrocarbons by Dioxygen Using Anthraquinones and N-Hydroxyphthalimide

Cu2O: a Simple and Efficient Reusable Catalyst for N-arylation of Nitrogen-containing Heterocycles with Aryl Halides

Facile preparation of highly-dispersed cobalt-silicon mixed oxide nanosphere and its catalytic application in cyclohexane selective oxidation.

Superhydrophobic materials as efficient catalysts for hydrocarbon selective oxidation.

Direct Synthesis of Bifunctionalized Hexagonal Mesoporous Silicas and Its Catalytic Performance for Aerobic Oxidation of Cyclohexane