Olefin metathesis or transalkylidenation (in some literature, a disproportionation) is an organic reaction which involves redistribution of olefinic (alkene) bonds. Since its discovery, olefin metathesis has gained widespread use in research and industry for making products ranging from medicines and polymers to enhanced fuels. Its advantages include the creation of fewer sideproducts and hazardous wastes. Yves Chauvin, Robert H. Grubbs, Richard R. Schrock shared the 2005 Nobel Prize in Chemistry for "the development of the metathesis method in organic synthesis".
The reaction is catalyzed by metals such as nickel, tungsten, ruthenium and molybdenum. The reaction consists of an alkene double bond cleavage, followed by a statistical redistribution of alkylidene fragments. The general scope is outlined by the following equation:
Olefin metathesis was first used in petroleum reformation for the synthesis of higher olefins from the products (α-olefins) from the Shell higher olefin process (SHOP) under high pressure and high temperatures. Many traditional catalysts are derived from a reaction of the metal halides with alkylation agents for example WCl6-EtOH-EtAlCl2. A metathesis reaction is a chain reaction that begins when a metallocarbene and an olefin react to form a metallacyclobutane. This intermediate then reacts further, decomposing into a new olefin (the product) and a new metallocarbene, which can then be recycled through the reaction pathway.
The Grubbs' catalyst is a ruthenium carbenoid, while molybdenum or tungsten catalysts are known as Schrock carbenes. These catalysts can also perform alkyne metathesis and related polymerizations.
The complete family of metathesis chemistry:
- Cross-metathesis (CM)
- Ring-closing metathesis (RCM)
- Enyne metathesis (EM)
- Ring opening metathesis (ROM)
- Ring opening metathesis polymerisation (ROMP)
- Acyclic diene metathesis (ADMET)
- Alkyne metathesis (AM)
- Alkane metathesis
- Alkene metathesis
Like most organometallic reactions, the metathesis pathway is usually driven by a thermodynamic imperative; that is, the final products are determined by the energetics of the possible products, with a distribution of products proportional to the exponential of their respective energy values.
Alkene metathesis is generally driven by the evolution of gaseous ethylene; and alkyne metathesis is driven by the evolution of acetylene. These are both dominated by the entropy gained by the net release of gas. Enyne metathesis cannot evolve a simple gas, and for that reason is usually disfavored unless there are accompanying ring-opening or ring-closing advantages. Ring opening metathesis usually involves a strained alkene (often a norbornene) and the release of ring strain drives the reaction. Ring-closing metathesis, conversely, usually involves the formation of a five- or six-membered ring which is highly energetically favorable; although these reactions tend to also evolve ethylene. RCM has been used to close larger macrocycles, in which case the reaction may be kinetically controlled by running the reaction at extreme dilutions. The Thorpe-Ingold effect may be exploited to improve both reaction rates and selectivity.
- Astruc D. (2005). ""The metathesis reactions: from a historical perspective to recent developments"" (abstract). New J. Chem. 29 (1): 42–56.
- "The Nobel Prize in Chemistry 2005" (Press release). Nobelprize.org. 5 Oct 2005.
- Ileana Dragutan*, Valerian Dragutan*, Petru Filip (2005). "Recent developments in design and synthesis of well-defined ruthenium metathesis catalysts – a highly successful opening for intricate organic synthesis".. 105. From Arkivoc.
- R.R. Schrock* (1986). "High-oxidation-state molybdenum and tungsten alkylidene complexes". Acc. Chem Res.
- A Recyclable Chiral Ru Catalyst for Enantioselective Olefin Metathesis. Efficient Catalytic Asymmetric Ring-Opening/Cross Metathesis in Air Joshua J. Van Veldhuizen, Steven B. Garber, Jason S. Kingsbury, and Amir H. Hoveyda J. Am. Chem. Soc.; 2002; 124(18) pp 4954 - 4955; (Communication) doi:10.1021/ja020259c
- Ione M. Baibich, Carla Kern (2002). ""Reactivity of Tungsten-aryloxides with Hydrosilane Cocatalysts in Olefin Metathesis"". Journal of the Brazilian Chemical Society. 13 (1): 43–46.
- "Olefin Metathesis: Big-Deal Reaction". Chemical & Engineering News. 80 (51): 29–33. 2002.
- "Olefin Metathesis: The Early Days". Chemical & Engineering News. 80 (51): 34–38. 2002.
- Schrock, R. R. (1990). "Living ring-opening metathesis polymerization catalyzed by well-characterized transition-metal alkylidene complexes". Acc. Chem. Res. 23 (5): 158–165. doi:10.1021/ar00173a007.
- Schrock, R. R. (2003). "Molybdenum and Tungsten Imido Alkylidene Complexes as Efficient Olefin-Metathesis Catalysts". Angew. Chem. Int. Ed. 42 (38): 4592–4633. doi:10.1002/anie.200300576. Unknown parameter
- Trnka, T. M. (2001). "The Development of L2X2Ru=CHR Olefin Metathesis Catalysts: An Organometallic Success Story". Acc. Chem. Res. 34 (1): 18–29. doi:10.1021/ar000114f. Unknown parameter
- Grubbs, R. H. (1998). "Recent advances in olefin metathesis and its application in organic synthesis". Tetrahedron. 54 (18): 4413–4450. doi:10.1016/S0040-4020(97)10427-6. Unknown parameter
- Grubbs, R. H. (2004). "Olefin metathesis". Tetrahedron. 60 (34): 7117–7140. doi:10.1016/j.tet.2004.05.124.