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.

/pdf/aerobic-copper-catalyzed-organic-reactions-3ctljpvivz.pdf

Aerobic Copper-Catalyzed Organic Reactions

Valorization of native birch wood lignin into monomeric phenols over nickel-based catalysts has been studied. High chemoselectivity to aromatic products was achieved by using Ni-based catalysts and common alcohols as solvents. The results show that lignin can be selectively cleaved into propylguaiacol and propylsyringol with total selectivity >90% at a lignin conversion of about 50%. Alcohols, such as methanol, ethanol and ethylene glycol, are suitable solvents for lignin conversion. Analyses with MALDI-TOF and NMR show that birch lignin is first fragmented into smaller lignin species consisting of several benzene rings with a molecular weight of m/z ca. 1100 to ca. 1600 via alcoholysis reaction. The second step involves the hydrogenolysis of the fragments into phenols. The presence of gaseous H2 has no effect on lignin conversion, indicating that alcohols provide active hydrogen species, which is further confirmed by isotopic tracing experiments. Catalysts are recycled by magnetic separation and can be reused four times without losing activity. The mechanistic insights from this work could be helpful in understanding native lignin conversion and the formation of monomeric phenolics via reductive depolymerization.

/pdf/lignin-depolymerization-ldp-in-alcohol-over-nickel-based-nu24mozrzq.pdf

Lignin depolymerization (LDP) in alcohol over nickel-based catalysts via a fragmentation–hydrogenolysis process

In view of the diminishing oil resources and the ongoing climate change, the use of efficient and environmentally benign technologies for the utilization of renewable resources has become indispensible. Therein, hydrogenolysis reactions offer a promising possibility for future biorefinery concepts. These reactions result in the cleavage of C-C and C-O bonds by hydrogen and allow direct access to valuable platform chemicals already integrated in today's value chains. Thus, hydrogenolysis bears the potential to bridge currently available technologies and future biomass-based refinery concepts. This Review highlights past and present developments in this field, with special emphasis on the direct utilization of cellulosic feedstocks.

Hydrogenolysis Goes Bio: From Carbohydrates and Sugar Alcohols to Platform Chemicals

Hypercrosslinked polymers (HCPs) are a series of permanent microporous polymer materials initially reported by Davankov, and have received an increasing level of research interest. In recent years, HCPs have experienced rapid growth due to their remarkable advantages such as diverse synthetic methods, easy functionalization, high surface area, low cost reagents and mild operating conditions. Judicious selection of monomers, appropriate length crosslinkers and optimized reaction conditions yielded a well-developed polymer framework with an adjusted porous topology. Post fabrication of the as developed network facilitates the incorporation of various chemical functionalities that may lead to interesting properties and enhance the selection toward a specific application. To date, numerous HCPs have been prepared by post-crosslinking polystyrene-based precursors, one-step self-polycondensation or external crosslinking strategies. The advent of these methodologies has prompted researchers to construct well-defined porous polymer networks with customized micromorphology and functionalities. In this review, we describe not only the basic synthetic principles and strategies of HCPs, but also the advancements in the structural and morphological study as well as the frontiers of potential applications in energy and environmental fields such as gas storage, carbon capture, removal of pollutants, molecular separation, catalysis, drug delivery, sensing etc.

Hypercrosslinked porous polymer materials: design, synthesis, and applications

Selective oxidation of primary carbon-hydrogen bonds with oxygen is of crucial importance for the sustainable exploitation of available feedstocks. To date, heterogeneous catalysts have either shown low activity and/or selectivity or have required activated oxygen donors. We report here that supported gold-palladium (Au-Pd) nanoparticles on carbon or TiO2 are active for the oxidation of the primary carbon-hydrogen bonds in toluene and related molecules, giving high selectivities to benzyl benzoate under mild solvent-free conditions. Differences between the catalytic activity of the Au-Pd nanoparticles on carbon and TiO2 supports are rationalized in terms of the particle/support wetting behavior and the availability of exposed corner/edge sites.

https://science.sciencemag.org/content/sci/331/6014/195.full.pdf

Solvent-Free Oxidation of Primary Carbon-Hydrogen Bonds in Toluene Using Au-Pd Alloy Nanoparticles

A new superhydrophobic material with cauliflower morphology was prepared with a one-step introduction of organic groups on the materials surface. Rough surface structure and heterogeneous surface chemical composition could be directly obtained. Adjustment of the phenyl group content was utilized to modulate the surface wettability, and different hydrophilic, hydrophobic, and superhydrophobic materials could be obtained by simply controlling the ratio of phenyl groups and silanols. The dynamic wettability of the superhydrophobic materials could be flexibly tuned between water repellent and water adhesive by the adjustment of the surface chemical composition. Especially the unique water-adhesive superhydrophobic material demonstrates capacity in solid and water transfer, and it may show wide application in the future.

http://www.rsc.org/suppdata/jm/c1/c1jm10283d/c1jm10283d.pdf

Preparation of superhydrophobic cauliflower-like silica nanospheres with tunable water adhesion

Fluoride-free and low concentration template synthesis of hierarchical Sn-Beta zeolites: efficient catalysts for conversion of glucose to alkyl lactate

Chen Chen

Papers

Preparation of superhydrophobic cauliflower-like silica nanospheres with tunable water adhesion

Fluoride-free and low concentration template synthesis of hierarchical Sn-Beta zeolites: efficient catalysts for conversion of glucose to alkyl lactate

Depolymerization of cellulose to glucose by oxidation–hydrolysis

A remarkable promoting effect of water addition on selective hydrogenation of p-chloronitrobenzene in ethanol

Hydrolysis of hemicellulose catalyzed by hierarchical H-USY zeolites – The role of acidity and pore structure