Author Archive

Catalytic mechanism of KI and co-catalytic mechanism of hydroxyl substances for cycloaddition of CO2 with propylene oxide

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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Frontiers in Biorefining 2012 – 30th October-2nd November

The 2nd International Conference ‘Frontiers in Biorefining‘ on Chemicals and Products from Renewable Carbon is being held between the 30th October-2nd November 2012 at the King and Prince Beach & Golf Resort, St Simons Island, Georgia USA. 

The event will be hosted by the University of Tennessee’s Centre for Renewable Carbon in partnership with the Southeastern Regional Sun Grant Centre, and will emphasize the latest developments on the transformation of renewable carbon building blocks to chemicals and materials, enabling the integrated biorefinery concept.  The tentative sessions planned for the event are:

  • Biorefinery concepts for chemicals and products
  • From pretreatment to fractionation
  • Chemicals from carbohydrates
  • Catalysis in the biorefinery
  • Advances in analytical techniques
  • Chemicals from lignin
  • Developing the industrial biorefinery

The deadline for submission of abstracts is the 17th August 2012 – click here for more details about the requirements and full instructions on how to submit.

Early Bird registration for the conference ends on the 15th August 2012 – to register, click here.

Visit the conference website for further information – http://www.fib2012.org/

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Renewable plasticizer alcohols by formal anti-Markovnikov hydration of terminal branched chain alkenes

Plasticizer alcohols have been synthesised from renewable reagents through a borane-free oxidation/reduction sequence.

Bis(2-ethyl-hexyl) phthalate (DEHP) is one of the most important and widely used industrial plasticizers and is generated from 2-ethyl-1-hexanol (2EH) and phthalic anhydride.  In the process of converting bio-butanol to jet fuels, a significant amount of 2-ethyl-1-hexene is produced as a by-product, and is an attractive feedstock to generate 2EH.  To yield the required 2EH from 2-ethyl-1-hexene, an anti-Markovnikov addition is required. However, the traditional hydroboration method used to achieve this is not ideal for large scale, atom economic production of 2EH.

In this work, Benjamin Harvey and colleagues from the United States Navy-Naval Air Systems Command (NAVAIR) demonstrate an efficient method for formal anti-Markovnikov hydration of 1,1-disubstituted alkenes.  Their approach generates the plasticizer alcohols by the oxidation/hydration/hydrogenation of branched chain alkenes under mild, borane-free conditions.  This process was successfully applied to the production of 2EH from 2-ethyl-1-hexene, and presents an alternative to hydroboration for a challenging subset of hindered olefins.

This article is free to access until the 29th August 2012!  Click on the link below to find out more…

Synthesis of renewable plasticizer alcohols by formal anti-Markovnikov hydration of terminal branched chain alkenes viaa borane-free oxidation/reduction sequence, Benjamin G. Harvey, Heather A. Meylemans and Roxanne L. Quintana, Green Chem., 2012, DOI: 10.1039/C2GC35595G

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Mechanism of efficient anti-Markovnikov olefin hydroarylation catalyzed by homogeneous Ir(III) complexes, Gaurav Bhalla, Steven M. Bischof, Somesh K. Ganesh, Xiang Yang Liu, C. J. Jones, Andrey Borzenko, William J. Tenn, III, Daniel H. Ess, Brian G. Hashiguchi, Kapil S. Lokare, Chin Hin Leung, Jonas Oxgaard, William A. Goddard, III and Roy A. Periana, Green Chem., 2011, 13, 69-81

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Cu-catalysed reductive amination of ketones with anilines using molecular hydrogen

Aromatic and aliphatic ketones reacted with aniline and molecular hydrogen in the presence of an easily available copper catalyst to give amines in high yields.

Reductive amination is one of the most important and effective C-N bond forming reactions and provides a general practical way to access amines.  The reaction commonly involves chemicals which act hydrogen donors to be present, such as silanes and formates.  However, utilizing molecular hydrogen instead would give a much more environmentally and atom-economical reducing agent, would give water as the only by-product.

Here, Matthias Beller and colleagues from the Leibniz-Institute for Catalysis in Rostock, Germany report that simple Cu(OAc)2, an inexpensive and easily available catalyst, could catalyse the reductive amination of a variety of ketones with anilines and molecular hydrogen.  The procedure does not require any complicated ligands or additional acid or base and represents the first example of a catalytic approach using copper and molecular hydrogen for reductive aminations.

This article is free to access until the 24th August 2012!  Click on the link below to find out more…

Copper-catalyzed reductive amination of aromatic and aliphatic ketones with anilines using environmental-friendly molecular hydrogen, Svenja Werkmeister, Kathrin Junge and Matthias Beller, Green Chem., 2012, DOI: 10.1039/C2GC35565E

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Issue 8 of Green Chemistry now online

The latest issue of Green Chemistry is now available online!

The front cover of issue 8 features work by Matthew Fuchter and co-workers from Imperial College London and Pfizer Ltd in Sandwich.  The team developed a route to give allylic alcohols from α,β-unsaturated ketones using calcium triflate to replace cerium(III) chloride.  This procedure also accomplished the regioselective 1,2-reduction of challenging α,β-unsaturated ketones such as 2-cyclopentenone with very good selectivity, and is suitable for the stereoselective reduction of α,β-aziridinyl ketones.

Lanthanide replacement in organic synthesis: Luche-type reduction of α,β-unsaturated ketones in the presence of calcium triflate, Nina V. Forkel, David A. Henderson and Matthew J. Fuchter, Green Chem., 2012, 14, 2129-2132.

The inside front cover highlights work by Man Bock Gu and colleagues from Korea University in Seoul, who report the carbonic anhydrase-assisted formation of biomineralized calcium carbonate crystalline composites (CCCCs).  These materials were shown to be effective biocatalysts retaining 43% of the free carbonic anhydrase esterase activity.  The catalysts were stable for more than 50 days at room temperature, could be recovered easily using magnet-based separation and retained their activity over 10 repeated usages.

Carbonic anhydrase assisted calcium carbonate crystalline composites as a biocatalyst, Ee Taek Hwang, Haemin Gang, Jinyang Chung and Man Bock Gu, Green Chem., 2012, 14, 2216-2220

These articles are free to access for 6 weeks

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Meet our Authors: Francesca Kerton

Francesca Kerton is Associate Professor of Green Chemistry at the Memorial University of Newfoundland, Canada.  Her research into green chemistry encompasses three main themes: catalysis (including organometallic chemistry), solvent replacement (including supercritical fluids) and renewable feedstocks.  Fran kindly spared a few moments to chat to Green Chemistry

Who or what initially inspired you to become a chemist?

When I was very young, like many other children, I played in the garden making mud-pies and would attempt to make perfumes using the flowers there. I always liked to get my hands dirty and was a bit of a tomboy. At the root of this, I think I really wanted to understand how things worked, what they were made from and if you could turn them into something else. So in that regard, nature was my inspiration. When I was older and began secondary school, some of our first practical classes involved separations and paper chromatography. These also included looking at isolating chlorophyll and other natural products from plants. My school had excellent chemistry teachers, who would go the extra mile to explain things and challenge the bright students. Most importantly, they made what we were learning relevant to everyday life. I have very fond memories of my GCSE and A-Level Chemistry teachers, Ms. Jones and Mr. Woodstock, and they definitely inspired me to pursue a career in chemistry.

What was the motivation behind the research described in your recent Green Chemistry article?

I have been interested in ‘green’ solvents for sometime and water, ionic liquids and carbon dioxide have all been used in my group recently. I relocated to Newfoundland in Canada from the UK in 2005. In the UK, I had been involved with the Green Chemistry Group at York and had just started to perform research using renewable feedstocks to make new materials and compounds. Historically, Newfoundland had a large fishing industry and it still has a vibrant fishing community, particularly in both catching and farming shellfish. I knew that this industry would produce a number of by-products and I was particularly interested in seeing whether we could add value to these. In particular, could chitin (the biopolymer in the shells of crustaceans) be depolymerized under green conditions and produce useful compounds? We also wanted to keep things cheap and simple, therefore, we decided to look at reactions of chitin and chitosan in water using commercially available catalysts. We found that the results with chitosan were not that different to those that had been obtained using cellulose as a feedstock, namely, we obtained levulinic acid and 5-hydroxymethylfurfural as the primary products (Green Chemistry, 2012, 14, 1480-1487).  This gives me some hope that ocean-sourced biomass can be used as a feedstock in future biorefineries alongside land-sourced materials.

What do you see as the main challenges facing research in this area?

Industrial implementation of new, green ideas is of course important for the success of this field. However, this could be helped if more industries were a little more transparent and made us aware of their real problems. I think the ACS GCI pharmaceutical roundtable has helped green chemists at universities focus their attention on real rather than imagined problems. It would be great to see this approach extended to other industries including those where perhaps the beneficial role that green chemistry could play is perhaps less obvious e.g. food industry and mining industry. Also, collaboration across the sub-disciplines is really important for the development of this field.  There are some problems here, for example, the units and language used by chemical engineers is different to that used by chemists – so we need to make an effort and be patient with each other in order to solve important problems and achieve our goals.

Where do you see the field of Green Chemistry being in 5 or 10 years time?

I am an optimist and see the field growing enormously and becoming a global endeavor. I see more collaborations across disciplines and the establishment of worldwide research networks to tackle some of the key problems of sustainability such as universal access to a clean water supply.

And finally…

If you could not be a scientist, but could be anything else, what would you be?

I love music. At high school and as an undergraduate, I sang in a band. I don’t think I would have had what it takes to do that for a living but I would have liked to be involved behind the scenes in the music industry or be a promoter of shows and concerts or an event planner.

Take a look at a couple of Fran’s recent Green Chemistry articles – free to access until the 8th August:

Hydrolysis of chitosan to yield levulinic acid and 5-hydroxymethylfurfural in water under microwave irradiation, Khaled W. Omari, Jessica E. Besaw and Francesca M. Kerton, Green Chem., 2012, 14, 1480-1487

Synthesis of Pd nanocrystals in phosphonium ionic liquids without any external reducing agents, Hassan A. Kalviri and Francesca M. Kerton, Green Chem., 2011, 13, 681-686

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Polyamide precursors from renewable 10-undecenenitrile and methyl acrylate via olefin cross-metathesis

French scientists report a ruthenium-catalysed cross-metathesis route to produce a C12 nitrile ester with high turnover number.

10-Undecylenic acid derivatives are a valuable feedstock readily available from caster oil and have been used for the industrial production of polyamide.  In this work, scientists from CBRS-University of Rennes and ARKEMA in France demonstrate that the linear C12 α,ω-amino ester, a precursor to polyamide, can be prepared viacross-metathesis of methyl acrylate with 10-undecenenitrile (which is bio-sourced) in the presence of ruthenium-alkylidene catalysts.  Subsequent C=C and nitrile reduction could then be performed to produce the C12 α,ω-amino ester.

This overall tandem procedure provides a sustainable route to linear amino esters, where a single catalyst is used from the outset to perform 3 catalytic transformations (cross-metathesis, carbon-carbon double bond hydrogenation and nitrile reduction) using bio-sourced starting materials.

This article is free to access until the 6th August 2012! Click on the link below to find out more…

Polyamide precursors from renewable 10-undecenenitrile and methyl acrylate via olefin cross-metathesis, X. Miao, C. Fischmeister, P. H. Dixneuf, C. Bruneau, J.-L. Dubois and J.-L. Couturier, Green Chem., 2012, DOI: 10.1039/C2GC35648A

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Ruthenium–alkylidene catalysed cross-metathesis of fatty acid derivatives with acrylonitrile and methyl acrylate: a key step toward long-chain bifunctional and amino acid compounds, X. Miao, R. Malacea, C. Fischmeister, C. Bruneau and P. H. Dixneuf, Green Chem., 2011, 13, 2911-2919

A green route to nitrogen-containing groups: the acrylonitrile cross-metathesis and applications to plant oil derivatives, Xiaowei Miao, Pierre H. Dixneuf, Cédric Fischmeister and Christian Bruneau, Green Chem., 2011, 13, 2258-2271

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Organic solvent nanofiltration: an alternative method for solvent recovery from crystallisation mother liquors

UK Scientists report the feasibility of solvent recovery via solvent nanofiltration as an alternative to distillation.

Distillation has been the common technique employed for separating solvent from crystallisation mother liquors for many years.  However, although high purity solvent is generated from this process, it can be very energy-intensive and so a low energy alternative is highly sort after.  Here, Christopher Pink and colleagues from GlaxoSmithKline R&D Ltd and Imperial College London, UK, report the use of organic solvent nanofiltration (OSN) as an alternative to distillation for solvent recovery.  The team report that OSN is capable of recovering the organic solvent with a purity suitable for re-use in subsequent crystallisation processes, and energy-efficiency calculations show that OSN uses 25 times less energy per L of recovered solvent compared to distillation. 

However, the efficiency of this membrane-based solvent recovery is restricted by the solubility of the compounds within the waste stream, and can result in the recovery of less solvent for OSN.  But equivalent recovery volumes can be obtained with a combined distillation/OSN approach, still resulting in 9 times less energy consumption than when using distillation alone. 

This article is free to access until the 31st July 2012!  Click on the link below to find out more…

Organic solvent nanofiltration: a potential alternative to distillation for solvent recovery from crystallisation mother liquors, Elin M. Rundquist, Christopher J. Pink and Andrew G. Livingston, Green Chem., 2012, DOI: 10.1039/C2GC35216H

You may also be interested in these articles – free to access for 2 weeks:

Environmentally friendly route for the preparation of solvent resistant polyimide nanofiltration membranes, Iwona Soroko, Yogesh Bhole and Andrew Guy Livingston, Green Chem., 2011, 13, 162-168

Product recovery from ionic liquids by solvent-resistant nanofiltration: application to ozonation of acetals and methyl oleate, Charlie Van Doorslaer, Daan Glas, Annelies Peeters, Angels Cano Odena, Ivo Vankelecom, Koen Binnemans, Pascal Mertens and Dirk De Vos, Green Chem., 2010, 12, 1726-1733

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Green Chemistry celebrates highest ever impact factor – 6.32

The release of the 2011 Thomson Scientific (ISI) Journal Citation Reports* sees Green Chemistry achieve an impact factor over 6 for the first time! 

The 2011 impact factor of 6.32 re-enforces Green Chemistry‘s position as one of the leading Journals in the field of sustainable chemistry and technology.

We would like to thank all our authors, referees, readers and Editorial and Advisory Board  members for their help and support on the Journal.

Join your colleagues and submit your research today!

Read more about the 2011 Impact Factors from across RSC Publishing on the RSC Publishing Blog.

*The Impact Factor provides an indication of the average number of citations per paper. Produced annually, Impact Factors are calculated by dividing the number of citations in a year, by the number of citeable articles published in the preceding two years. Data based on 2011 Journal Citation Reports®, (Thomson Reuters, 2012).

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Green Chemistry issue 7 – now online!

The latest issue of Green Chemistry is now available online and is packed with the usual high quality research.

The front cover of this issue showcases the Critical Review by Raffael Wende and Peter Schreiner from Justus-Liebig University in Giessen, Germany, on the evolution of asymmetric organocatalysis.  The authors focus on the recent developments into organomulticatalysis, i.e.the combination of several distinct organocatalysts enabling consecutive reactions to be conducted in one pot. Schreiner and Wende also look at multicatalysts – catalysts with a single backbone with several independent, orthogonally reactive moieties attached.  The review highlights the impressive advantages of asymmetric organomulticatalysis and look at the development that have occurred from it’s very beginnings to the latest multicatalyst systems. 

Evolution of asymmetric organocatalysis: multi- and retrocatalysis, Raffael C. Wende and Peter R. Schreiner, Green Chem., 2012, 14, 1821-1849

The inside front cover highlights work by Hong Liu and colleagues from the Shanghai Institute of Materia Medica, Chinese Academy of Sciences, China, who reported the gold catalysed synthesis of fused polycyclic indoles.  Substituted 2-(1H-indol-1-yl)alkylamines were reacted with alkynoic acids in water under microwave irradiation for 30 min giving the products in excellent yields.  This procedure proceeds with high atom economy and leads to the generation of two rings, together with the formation of one new C-C bond and two new C-N bonds in a single operation. 

Gold-catalyzed tandem reaction in water: an efficient and convenient synthesis of fused polycyclic indoles, Enguang Feng, Yu Zhou, Fei Zhao, Xianjie Chen, Lei Zhang, Hualiang Jiang and Hong Liu, Green Chem., 2012, 14, 1888-1895

These articles are free to access for 6 weeks

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