4.3. Reaction Mechanism 2373 4.4. Asymmetric Synthesis 2374 4.5. Outlook 2374 5. Alternating Polymerization of Oxiranes and CO2 2374 5.1. Reaction Outlines 2374 5.2. Catalyst 2376 5.3. Asymmetric Polymerization 2377 5.4. Immobilized Catalysts 2377 6. Synthesis of Urea and Urethane Derivatives 2378 7. Synthesis of Carboxylic Acid 2379 8. Synthesis of Esters and Lactones 2380 9. Synthesis of Isocyanates 2382 10. Hydrogenation and Hydroformylation, and Alcohol Homologation 2382

Transformation of carbon dioxide.

Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels. technological use of CO2.

The increase in atmospheric carbon dioxide is linked to climate changes; hence there is an urgent need to reduce the accumulation of CO2 in the atmosphere. The utilization of CO2 as a raw material in the synthesis of chemicals and liquid energy carriers offers a way to mitigate the increasing CO2 buildup. This review covers six important CO2 transformations namely: chemical transformations, photochemical reductions, chemical and electrochemical reductions, biological conversions, reforming and inorganic transformations. Furthermore, the vast research area of carbon capture and storage is reviewed briefly. This review is intended as an introduction to CO2, its synthetic reactions and their possible role in future CO2 mitigation schemes that has to match the scale of man-made CO2 in the atmosphere, which rapidly approaches 1 teraton.

The teraton challenge. A review of fixation and transformation of carbon dioxide

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 need to reduce the accumulation of CO2 into the atmosphere requires new technologies able to reduce the CO2 emission. The utilization of CO2 as a building block may represent an interesting approach to synthetic methodologies less intensive in carbon and energy. In this paper the general properties of carbon dioxide and its interaction with metal centres is first considered. The potential of carbon dioxide as a raw material in the synthesis of chemicals such as carboxylates, carbonates, carbamates is then discussed. The utilization of CO2 as source of carbon for the synthesis of fuels or other C1 molecules such as formic acid and methanol is also described and the conditions for its implementation are outlined. A comparison of chemical and biotechnological conversion routes of CO2 is made and the barriers to their exploitation are highlighted.

Utilisation of CO2 as a chemical feedstock: opportunities and challenges

Selective Conversion of Carbon Dioxide to Dimethyl Carbonate by Molecular Catalysis.

Conversion of carbon dioxide to industrially useful compounds has been a challenge for synthetic chemists and has recently attracted much interest One of the most attractive synthetic goals starting from CO{sub 2} is dimethyl carbonate (DMC) Indeed, the straightforward reaction of methanol and CO{sub 2} catalyzed by R{sub 2}Sn(OMe){sub 2} leading to DMC has been intensively studied although catalytic performance is still far from satisfactory The authors have recently enhanced the catalytic efficiency of R{sub 2}Sn(OMe){sub 2} using dehydrated derivatives of methanol (eg, ortho esters and acetals) as a starting material under supercritical CO{sub 2} conditions

Reaction of Dialkyltin Methoxide with Carbon Dioxide Relevant to the Mechanism of Catalytic Carbonate Synthesis

Synthesis of dimethyl carbonate from carbon dioxide: catalysis and mechanism

Metal-Catalyzed Dimethyl Carbonate Synthesis from Carbon Dioxide and Acetals

PROBLEM TO BE SOLVED: To provide a method of producing a carbonate in an industrially advantageous manner, in which decomposition reaction of a catalyst by by- produced water and hydrolysis reaction (reverse reaction) are suppressed and, a desired carbonate can be obtained in an increased yield and the reaction can be carried out in a homogeneous system capable of readily controlling the reaction operation. SOLUTION: This method of producing a carbonate comprises combining (i) a step for reacting an alcohol with carbon dioxide in the presence of a metal catalyst to obtain the carbonate with (ii) a step for cooling the reaction solution obtained from the above reaction step, (iii) a step for dehydrating the reaction solution cooled by the above cooling step and (iv) a step for recycling the reaction solution dehydrated by the dehydration step to the above reaction step (i).

Takeshi Sako

Papers

Selective Conversion of Carbon Dioxide to Dimethyl Carbonate by Molecular Catalysis.

Reaction of Dialkyltin Methoxide with Carbon Dioxide Relevant to the Mechanism of Catalytic Carbonate Synthesis

Synthesis of dimethyl carbonate from carbon dioxide: catalysis and mechanism

Metal-Catalyzed Dimethyl Carbonate Synthesis from Carbon Dioxide and Acetals

Method of producing carbonate from carbon dioxide and alcohol