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Olefin Metathesis in Aqueous Media Offers a New, Broad M Green Chemistry CRITICAL REVIEW View Article Online View Journal | View Issue Olefin metathesis in aqueous media Cite this: Green Chem., 2013, 15, 2317 Jasmine Tomasek and Jürgen Schatz* The worldwide undisputable and unattainable chemist is nature, using water as a solvent of choice in biosynthesis. Water as a solvent not only indicates “green chemistry” but is also inevitable in biochemical reactions as well as syntheses of several pharmaceutical products. In the last few decades, several organic reactions were successfully carried out under aqueous conditions, a powerful and attractive tool in Received 3rd June 2013, organic synthesis metathesis reaction. This review summarises advances made in metathesis reaction in Accepted 12th July 2013 aqueous media. Two main strategies can be distinguished: the design of water soluble catalysts to obtain DOI: 10.1039/c3gc41042k homogeneous conditions and using commercially available catalysts to utilize the advantages of hetero- www.rsc.org/greenchem geneous conditions. reactions, meaning coupling reactions of cyclic and acyclic Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Introduction alkenes or alkynes as well as polymerisation reactions In organic chemistry, C–C coupling reactions open a wide (Scheme 1).1 Accordingly, the metathesis has been of great range of applications for effective synthesis, which otherwise interest since its discovery in the mid-1950s3 and reveals a would be difficult or even hardly feasible. The olefin meta- powerful tool for both industrial applications, especially in thesis reaction displays one of these atom efficient catalysis petro- and polymer chemistry and organic synthesis.4,5 reactions under mild conditions.1 The term “olefin meta- Already in 1966, one of the first metathesis applications thesis” was coined by Calderon and displays a catalytic reaction was carried out on an industrial scale, the Philips-triolefin- where “olefins undergo bond reorganization, resulting in a process,4a years before the mechanism and the role of the cata- 2 This article is licensed under a redistribution of alkylidene moieties”. This C–C double-bond lyst were unambiguously elucidated. While several research transformation reaction includes not only one kind of reaction, groups dealt with this topic and suggested a pair-wise inter- but also a wide variety of different types of metathesis change of the alkylidene moieties,6 Chauvin postulated a more Open Access Article. Published on 15 July 2013. Downloaded 10/2/2021 4:12:26 AM. complex catalytic cycle, which displays the generally accepted and Nobel-Prize honoured mechanism (Scheme 2).7,8 The Organic Chemistry 1 and ICMM (Interdisciplinary Center for Molecular Materials), ff University Erlangen-Nuremberg, Henkestr. 42, D-91054 Erlangen, Germany. main di erence is the assumption that there is no direct alkyli- E-mail: [email protected]; Fax: +49 9131 85-24707; Tel: +49 9131 85-25766 dene exchange between the olefins, but a transfer via the Jasmine Tomasek studied chem- In 1994 Jürgen Schatz completed istry at the Friedrich-Alexander his Ph.D. in Organic Chemistry University (FAU) of Erlangen- under the guidance of Jürgen Nuremberg and obtained an Sauer at the University of M.Sc. in Chemistry in 2011. Regensburg. After a postdoctoral After this, she joined the research stay with C. W. Rees, CBE FRS, group of J. Schatz and is perus- at the Imperial College, London, ing her Ph.D. research related to he returned to Germany to start the application of supramolecu- his independent career at the lar chemistry in aqueous olefin University of Ulm. After one metathesis reactions. semester at LMU Munich 2007, he moved to his current position Jasmine Tomasek Jürgen Schatz at the Friedrich-Alexander Uni- versity (FAU) of Erlangen-Nurem- berg. His research is focused on supramolecular chemistry and its use in catalytic processes with a focus on water as a solvent. This journal is © The Royal Society of Chemistry 2013 Green Chem., 2013, 15, 2317–2338 | 2317 View Article Online Critical Review Green Chemistry Table 1 Affinity of transition metal catalysts to different functional groups10 Ti W Mo Ru Alcohols, Alcohols, Alcohols, Olefins H2O H2O H2O Acids Acids Acids Alcohols, H2O Aldehydes Aldehydes Aldehydes Acids Ketones Ketones Olefins Aldehydes Esters, Olefins Ketones Ketones amides Olefins Esters, Esters, Esters, amides amides amides the efficiency of the catalytic reaction. For supported catalysts a pre-treatment step is needed, which requires harsh con- ditions. Otherwise, in many cases the initiation step is very Scheme 1 Variety of olefin metathesis reactions. Cross metathesis (CM), ring- slow and leads to a low concentration of the metathesis active closing metathesis (RCM), ring-opening metathesis (ROM), ring-opening cross metathesis (ROCM), ring-opening metathesis polymerisation (ROMP), acyclic catalyst. Additionally, in polymerisation reactions it is some- dienmetathesis polymerisation (ADMET). times hard to control the propagating step. For these reasons the focus of catalyst design switched to single component cata- lysts, based on metal–carbene centres. First improvements of such carbene complexes are related to polymerisation experi- ments. Thereby carbene catalysts based on various metals Creative Commons Attribution-NonCommercial 3.0 Unported Licence. showed all living ring-opening metathesis (ROMP).10 To prevent unwanted side reactions or interactions with the metal centre, which interfere with the catalytic activity, metals with high functional group tolerance are needed. Grubbs generated a reactivity table based on the results of ROMP and other organic reactions, using titanium, tungsten, molybdenum and ruthenium as the metal centre (Table 1).10 Olefins, compared to aldehydes, ketones and esters, preferentially belong to soft This article is licensed under a functional groups. Taking this into account, it is not surpris- ing that ruthenium as the softest metal, i.e. the metal with most d-electrons, shows the highest affinity to olefins and con- sequently a high tolerance to functional groups as a meta- Open Access Article. Published on 15 July 2013. Downloaded 10/2/2021 4:12:26 AM. Scheme 2 Chauvin-mechanism of a CM. thesis catalyst. The best-known well-defined (pre)catalysts were prepared in the 1990s, based on molybdenum and ruthenium as early tran- catalyst by building a metal carbene complex III. The catalytic sition metals (Fig. 1). While the Schrock catalyst exhibits high activity, the tolerance to functional groups is very limited and cycle consists of sequential [2 + 2] cycloaddition reactions fol- 11 lowed by rearrangement of the double bonds. This mechanism the sensitivity to moisture and air is high. Five coordinated, includes fully reversible steps. To avoid a consequential ruthenium based Grubbs catalysts partially overcome these dis- advantages and are now an attractive tool for practical appli- mixture of olefins and to obtain only the desired product, a 12,13 shift of the equilibrium in the desired direction is crucial. cations. Especially the insertion of N-heterocyclic carbene Tailor-made catalysts are crucial for an optimized chemical (NHC) ligands is conducive to pre-catalysts with high meta- thesis activity and high tolerance to functional groups, air and reaction. At the beginning of metathesis research, catalysts 14 usually consisted not only of a single component, but com- moisture. As a result of these accomplishments, ruthenium ff 9 and NHC based pre-catalysts serve as a promising basic frame- monly of two or even three di erent species. In those cases 15,16 the active catalyst was generated in situ by mixing transition work in the followed catalyst design. metal halides and main group metal alkyls as co-catalysts, Organic reactions in aqueous media such as WCl6/EtAlCl2/EtOH, WOCl4/EtAlCl2, MoCl5/Et3Al, 9 ReCl5/EtAlCl2, to name only a few. In other cases catalysts Simultaneously with the development of metathesis reaction, a based on transition metals were supported on metal–oxide sur- trend towards water as a solvent in organic reactions has 17 faces, such as Al2O3 and SiO2, or were bound chemically on been evolving for several decades. Water is termed as a polymers.9 However, there are a number of factors influencing “green solvent”. This includes a lot of advantages over conven- the formation of the active species and therefore influencing tionally used organic solvents. Water is economical and safe, 2318 | Green Chem., 2013, 15, 2317–2338 This journal is © The Royal Society of Chemistry 2013 View Article Online Green Chemistry Critical Review Scheme 3 Decomposition of Grubbs precatalysts 1b to monohydride species 4 in the presence of methanol.27 monohydride species (Scheme 3), which can now act as α-olefin isomerization catalysts.27b In contrast to alcohols, water leads to other unknown products and oxygen leads to the formation of both the monohydride species and another Fig. 1 Schrock, Grubbs 1st generation 1, Grubbs 2nd generation 2 and decomposition compound. Nevertheless, these results seemed Hoveyda–Grubbs 3 (pre)catalysts. not to interfere with metathesis reactions performed in water. All discussed decomposition reactions only occur at elevated temperatures and after a prolonged reaction time. Therefore, Creative Commons Attribution-NonCommercial 3.0 Unported Licence. and it is neither flammable, potentially explosive, mutagenic, such processes should not be completely ignored, but can “ ” nor carcinogenic. Otherwise, the term green also indicates a usually be neglected
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