Recyclable metathesis catalysts

Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing

Reexamination Certificate

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C502S103000, C502S125000, C502S162000, C502S156000

Reexamination Certificate

active

06921735

ABSTRACT:
Highly active, recoverable and recyclable transition metal-based metathesis catalysts and their organometallic complexes including dendrimeric complexes are disclosed, including a Ru complex bearing a 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene and styrenyl ether ligand. The heterocyclic ligand significantly enhances the catalytic activity, and the styrenyl ether allows for the easy recovery of the Ru complex. Derivatized catalysts capable of being immobilized on substrate surfaces are also disclosed. The present catalysts can be used to catalyze ring-closing metathesis (RCM), ring-opening (ROM) and cross metatheses (CM) reactions, and promote the efficient formation of various trisubstituted olefins at ambient temperature in high yield.

REFERENCES:
Kingsburg et al., “A recyclable Ru-based metathesis catalyst”, J.Am.Chem.Soc., 121(4), 791-799(1998).
Harrity et al., “Chromenes through metal-catalyzed reactions of styrenyl ethers, mechanism and utility in synthesis”, J.Am.Chem.Soc., 120(10), 2343-2351(1997).
Garber et al., “Efficient and recyclable monomeric and dendritic Ru-based metathesis catalysis”, J.Am.Chem.Soc., 122(34), 8168-8179(2000).
Garber, et al., Efficient and Recyclable Monomeric and Dendritic Ru-Based Metathesis Catalysts,Journal of the American Chemical Society, vol. 122, No. 34: 8168-8179 (2000).
Kingsbury, et al., A Recyclable Ru-Based Metathesis Catalyst,Journal of the American Chemical Society, vol. 121, No. 4: 791-799 (1998).
Gessler, et al., Synthesis and Metathesis Reactions of a Phosphine-free Dihydroimidazole Carbene Ruthenium Complex,Tetrahedron Letters, No. 51: 9973-9976 (2000).
Harrity, et al., Chromenes through Metal-Catalyzed Reactions of Styrenyl Ethers, Mechanism and Utility in Synthesis,Journal of the American Chemical Soceity, vol. 120, No. 10: 2343-2351 (1997).
Randl, et al., Highly Selective Cross Metathesis with Acrylonitrile Using a Phosphine Free Ru-Complex,Synlett, No. 3: 430-432 (2000).
Harrity, et al., Ru-Catalyzed Rearrangement of Styrenyl Ethers. Enantioselective Synthesis of Chromenes through Zr- and Ru-Catalyzed Processes,Journal of the American Chemical Society, vol. 119; 1488-1489 (1996).
International Search Report PCT/US01/24955.

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