Recent Advances in Alkene and Alkyne Metathesis Reaction

 

 

Karol Grela

 

Institute of Organic Chemistry, Polish Academy of Sciences, Warsaw, Poland

 

 

The development of well-accessible second generation Grubbs' olefin metathesis catalysts combining high activity with an excellent tolerance to a variety of functional groups has been key to the widespread application of olefin metathesis in organic synthesis and polymer chemistry.

 

Although the reactivity of  Ru-catalysts towards some substrates is well documented, this area is far from being fully explored. The syntheses of some new air-stable ruthenium complexes based on the Hoveyda-Grubbs complex and their applications in metathesis of several "problematic" substrates, such as a,b-unsaturated compounds will be presented. The reactivity of such catalysts can  be easily adjusted by changing electronic and steric properties of the  ligands.

 

An improved instant catalyst for alkyne metathesis reaction will be described. Catalyst formed in situ from molybdenum hexacarbonyl and 2-fluorophenol can be used without exclusion of air and moisture and shows high activity in alkyne cross-metathesis and ring-closing alkyne metathesis of functionalized diynes.

 

 

1.        Harutyunyan; S., Michrowska, A.; Grela, K. "A Highly Active Ruthenium (Pre)catalyst for Metathesis Reactions" in Catalysts for Fine Chemical Synthesis, Vol. 3, (Ed. S. Roberts), Wiley Interscience, 2004, in print

2.        Demchuk, O. M.; Pietrusiewicz, K. M.; Michrowska, A.; Grela, K. "Synthesis of Substituted P-Stereogenic Vinylphosphine Oxides by Olefin Cross-Metathesis" Org. Lett. 2003, 5, 3217-3220.

3.        Grela, K.; Michrowska, A.; Bieniek, M.; Kim, M.; Klajn, R. "Cross-metathesis reaction of vinyl sulfones and sulfoxides" Tetrahedron 2003, 59, 4525-4531.

4.        Grela, K.; Kim, M. "Good Bargain: An Inexpensive Air-Stable Ruthenium Metathesis Catalyst Derived from Asarone" Eur. J. Org. Chem. 2003, 963-966.

5.        Grela, K.; Harutyunyan; S., Michrowska, A. "A New Highly Efficient Ruthenium Catalyst for Metathesis Reaction" Angew. Chem. Int. Ed. 2002, 41, 4038-4040 (Angew. Chem. 2002, 114, 4210-4212)

6.        Grela, K.; Ignatowska, J. "An Improved Catalyst for Ring Closing Alkyne Metathesis Based on Molybdenum Hexacarbonyl/2-Fluorophenol" Org. Lett. 2002, 4, 3747-3749.