Study of the Activity and Stereoselectivity of Some Metathesis Catalysts with Acyclic Internal Olefins
The stereochemistry of the olefin metathesis has been the subject of numerous publications which tried to rationalize the behaviour of various catalysts with acyclic olefins [1-5]. It had been noticed during these studies that a cis olefin gave preferentially a cis olefin and that a trans olefin led essentially to a trans olefin. This was explained in terms of stability of the metallacyclobutanes involved in the catalytic cycle (Scheme 1): the most favoured metallacyclobutanes are those where the substituents in positions 1 and 3 are equatorial. This simple rule allowed the explanation of most experimental results and the configuration retention.
KeywordsArgon Tungsten Molybdenum Alkene Ruthenium
Unable to display preview. Download preview PDF.
- 4.Basset, J.M., Boutarfa, D., Custodero, E., Leconte, M. and Paillet, C. (1990) The stereochemistry of metathesis of acyclic and cyclic olefins, in Y. Imamoglu (ed.), Olefin Metathesis and Polymerization Catalysts, Kluwer Academic Publishers, Dordrecht, pp. 45–88.Google Scholar
- 5.Leconte, M. and Basset, J.M. (1979) Nouv. J. Chim. 3, 429–431.Google Scholar
- 9.Fürstner, A. (1998) Ruthenium-catalyzed metathesis reactions in organic synthesis, in A. Fürstner (ed.), Alkene Metathesis in Organic Synthesis, Springer, Berlin, pp. 37–72.Google Scholar
- 14.Pagano, S. (1995) Métathèse d’oléfines soufrées. Application à l’obtention de thiophènes, Thesis, Lyon, N° 249–95.Google Scholar
- 15.Lefebvre, F. (2001) Ab initio study of the interaction of ruthenium alkylidene complexes with olefins: Differences between cis and trans olefins, unpublished results.Google Scholar
- 18.Schrock, R.R. (1998) Olefin metathesis by well-defined complexes of molybdenum and tungsten, in A. Fürstner (ed.), Alkene Metathesis in Organic Synthesis, Springer, Berlin, pp. 1–36.Google Scholar