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Scientists from Denmark and the USA have achieved efficient conversion of 5-hydroxymethylfurfural (HMF) to valuable chemicals over a Cu-doped porous metal oxide catalyst in supercritical methanol.

HMF (readily obtained from hexose sugars) has been identified as a key platform compound to generate useful renewable chemicals for the fuel industry, such as 2,5-dimethylfuran (DMF) and 2,5-dimethyltetrahydrofuran (DMTHF).  However, achieving selective transformation of HMF to a specific product and preventing the formation of undesired side-products remains a challenge.

In this work, a collaboration between scientists at the Technical University of Denmark, Yale University (USA) and the University of California Santa-Barbara (USA) led by Katalin Barta and Andreas Riisager have developed an one-pot procedure for the reduction of HMF.  The catalyst was prepared in aqueous solution from inexpensive and earth-abundant starting materials before undergoing calcination.  By tuning the reaction temperature, DMF or DMTHF and 2-hexanol could be obtained as the major products, and no formation of higher boiling side products or undesired char was detected. 

This article is free to access until the 28th September 2012!  Click on this link below to fine out more…

One-pot reduction of 5-hydroxymethylfurfural viahydrogen transfer from supercritical methanol, Thomas S. Hansen, Katalin Barta, Paul T. Anastas, Peter C. Ford and Anders Riisager, Green Chem., 2012, 14, 2457-2461

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Synergy of boric acid and added salts in the catalytic dehydration of hexoses to 5-hydroxymethylfurfural in water, Thomas S. Hansen, Jerrik Mielby and Anders Riisager, Green Chem., 2011, 13, 109-114

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Chinese scientists provide a clear picture of the cycloaddition of carbon dioxide (CO₂) and epoxides promoted by the KI/hydroxyl catalytic system.

Over recent years, the KI/hydroxyl catalytic system has been recognised as one of the most successful and important routes to convert CO₂ into value-added chemicals; for example, cyclic carbonates.  However, the catalytic mechanism is not clear.  In this work, Buxing Han and colleagues from the Chinese Academy of Sciences, Beijing, China, demonstrate a theoretical approach to clarify the catalytic mechanism of KI and the co-catalytic mechanism of hydroxyl substances.  The authors employed density functional theory method to determine the transition structures, rate-determining steps and lowest energy barrier reaction pathways for both gas phase and solvent conditions.  It was found that a ternary synergistic catalytic system was formed between the hydroxyl groups, the potassium cation and the iodine anion, I^––(–OH)–K⁺.

This article is free to access until the 4th September 2012!  Click on the link below to find out more…

The catalytic mechanism of KI and the co-catalytic mechanism of hydroxyl substances for cycloaddition of CO₂ with propylene oxide, Jun Ma, Jinli Liu, Zhaofu Zhang and Buxing Han, Green Chem., 2012, DOI: 10.1039/C2GC35711A

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One-pot conversion of CO₂ and glycerol to value-added products using propylene oxide as the coupling agent, Jun Ma, Jinliang Song, Huizhen Liu, Jinli Liu, Zhaofu Zhang, Tao Jiang, Honglei Fan and Buxing Han, Green Chem., 2012, 14, 1743-1748

Organotin-oxomolybdate coordination polymer as catalyst for synthesis of unsymmetrical organic carbonates, Jinliang Song, Binbin Zhang, Tainbin Wu, Guanying Yang and Buxing Han, Green Chem., 2011, 13, 922-927

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