A plethora of methods have been developed over the years so that carbon dioxide can be used as a reactant in organic synthesis. Given the abundance of this compound, its utilization in synthetic chemistry, particularly on an industrial scale, is still at a rather low level. In the last 35 years, considerable research has been performed to find catalytic routes to transform CO(2) into carboxylic acids, esters, lactones, and polymers in an economic way. This Review presents an overview of the available homogeneous catalytic routes that use carbon dioxide as a C(1) carbon source for the synthesis of industrial products as well as fine chemicals.

Transformation of Carbon Dioxide with Homogeneous Transition-Metal Catalysts: A Molecular Solution to a Global Challenge?

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

For green and sustainable chemistry, molecular oxygen is considered as an ideal oxidant due to its natural, inexpensive, and environmentally friendly characteristics, and therefore offers attractive academic and industrial prospects. This critical review introduces the recent advances over the past 5 years in transition-metal catalyzed reactions using molecular oxygen as the oxidant. This review highlights the scope and limitations, as well as the mechanisms of these oxidation reactions (184 references).

Recent advances in transition-metal catalyzed reactions using molecular oxygen as the oxidant

ZnO, aside from TiO2, has been considered as a promising material for purification and disinfection of water and air, and remediation of hazardous waste, owing to its high activity, environment-friendly feature and lower cost. However, their poor visible light utilization greatly limited their practical applications. Herein, we demonstrate the fabrication of different aspect ratios of the ZnO nanorods with surface defects by mechanical-assisted thermal decomposition method. The experiments revealed that ZnO nanorods with higher aspect ratio and surface defects show significantly higher photocatalytic performances.

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Effect of aspect ratio and surface defects on the photocatalytic activity of ZnO nanorods

This Review describes the application of nitroxides to synthesis and polymer chemistry. The synthesis and physical properties of nitroxides are discussed first. The largest section focuses on their application as stoichiometric and catalytic oxidants in organic synthesis. The oxidation of alcohols and carbanions, as well as oxidative C-C bond-forming reactions are presented along with other typical oxidative transformations. A section is also dedicated to the extensive use of nitroxides as trapping reagents for C-centered radicals in radical chemistry. Alkoxyamines derived from nitroxides are shown to be highly useful precursors of C-centered radicals in synthesis and also in polymer chemistry. The last section discusses the basics of nitroxide-mediated radical polymerization (NMP) and also highlights new developments in the synthesis of complex polymer architectures.

Nitroxides: applications in synthesis and in polymer chemistry.

An effective catalytic system comprising a 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) functionalized imidazolium salt ([Imim-TEMPO] + X - ), a carboxylic acid substituted imidazolium salt ([Imim-COOH] + X - ), and sodium nitrite (NaNO 2 ) was developed for the aerobic oxidation of aliphatic, allylic, heterocyclic and benzylic alcohols to the respective carbonyl compounds with excellent selectivity up to > 99%, even at ambient conditions. Notably, the catalyst system could preferentially oxidize a primary alcohol to the aldehyde rather than a secondary alcohol to the ketone. Moreover, the reaction rate is greatly enhanced when a proper amount of water is present. And a high turnover number (TON 5000) is achieved in the present transition metal-free aerobic catalytic system. Additionally, the functionalized imidazolium salts are successfully reused at least four times. This process thus represents a greener pathway for the aerobic oxidation of alcohols into carbonyl compounds by using the present task-specific ionic liquids in place of the toxic and volatile additive, such as hydrogen bromide, bromine, or hydrogen chloride (HBr, Br 2 or HCl), which is commonly required for the transition metal-free aerobic oxidation of alcohols.

TEMPO and Carboxylic Acid Functionalized Imidazolium Salts/Sodium Nitrite: An Efficient, Reusable, Transition Metal-Free Catalytic System for Aerobic Oxidation of Alcohols

The development of catalytic methods for chemical transformation of CO 2 into use- ful compounds is of paramount importance from a standpoint of C1 chemistry and so-called green chemistry. The kinetic and thermodynamic stability of CO 2 molecule presents signifi- cant challenges in designing efficient chemical transformations based on this potential feed- stock. In this context, efforts to convert CO 2 to useful chemicals will inevitably rely on its activation through molecular catalysts, particularly transition-metal catalysts. Two prepara- tive processes employing solid catalyst or CO 2 -philic homogeneous catalyst were devised for environmentally benign synthesis of organic carbonates and oxazolidinones under solvent- free conditions. Those processes represent pathways for greener chemical fixations of CO 2 to afford industrial useful materials such as organic carbonates and oxazolidinones with great potential applications.

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Carbon dioxide chemistry: Examples and challenges in chemical utilization of carbon dioxide

A reversible in situ acidic catalytic system comprising recyclable TEMPO functionalized imidazolium salt ([Imim-TEMPO][Cl])/NaNO2/CO2/H2O was developed for selective transformation of a series of a...

Jing-Lun Wang

Papers

TEMPO and Carboxylic Acid Functionalized Imidazolium Salts/Sodium Nitrite: An Efficient, Reusable, Transition Metal-Free Catalytic System for Aerobic Oxidation of Alcohols

Carbon dioxide chemistry: Examples and challenges in chemical utilization of carbon dioxide

Self-Neutralizing in Situ Acidic CO2/H2O System for Aerobic Oxidation of Alcohols Catalyzed by TEMPO Functionalized Imidazolium Salt/NaNO2

A CO2/H2O2-tunable reaction: direct conversion of styrene into styrene carbonate catalyzed by sodium phosphotungstate/n-Bu4NBr

Ethylene carbonate as a unique solvent for palladium-catalyzed Wacker oxidation using oxygen as the sole oxidant