What is the history, scope + limitations, and utility of the alkene metathesis reaction?

History4

The alkene metathesis reaction (also known as the olefin metathesis) the “stitching together” of alkenes in a molecule. The reaction was first discovered by chemists in petrochemical companies like DuPont where they observed norborene being converted to polynorborene through the movement of the alkene. Researchers remarked how it looked like someone cut open the molecule and sewed it back together to form these polymers. It was researchers at Goodyear Tire and Rubber Company in 1967 who figured out that the double bond (olefin) was being cleaved and reformed in a different part of the molecule. However the mechanism for this reaction was not discovered until later. In 1971, Yves Chauvin and Jean-Louis Hérisson at the French petroleum institute proposed the idea that it was a metal carbene complex which is responsible for this olefin metathesis. A metal carbene complex involves an organic ligand coordinated to a transition metal. Thomas Katz, in 1975, observed a metal carbene complex perform olefin metathesis

which supported the mechanism that Yves Chauvin proposed. Finally it was Robert Grubbs and Richard Schrock who were able to synthesize the catalysts in the 1990’s involving transition metals  that were able to perform alkene metathesis such as the Grubbs II reagent used in this reaction. Chauvin, Schrock, and Grubbs were awarded the Nobel Prize in 2005 for the developing the alkene metathesis reaction.

There are generally Fischer carbene intermediates that formed as a result of using the Grubbs and Schrock catalysts. However, these Fischer carbene intermediates are often slow reacting and show easy deactivation via the formation of the corresponding carbide species. However, the Fischer intermediates that are stable, their equilibrium lies far to the right, so they balance out the scope of the reaction. The stable Fischer intermediates are more thermodynamically stable than the original starting materials.

The olefin metathesis reaction can be utilized in a wide variety of reactions from the synthesis of pharmaceutical drugs to applications in the petroleum industry. In terms of the development of pharmaceutical drugs, synthesis of a protease inhibitor for the hepatitis C virus1. Applications to the petroleum industry include the Shell higher olefin process which was developed by the Royal Dutch Shell Company and utilizes the olefin metathesis reaction to develop the precursors of detergents3

1. Lutz, E. F. Am. Chem. Soc. 1986, 63, 202-203.

3. MacNaughtan, M. L.; Brannon, G.; Deidra, L.; Gerlach, M. J. A. J.; Kampf, J.W. Organometallics, 2009, 28, 2880-2887.