Claims
- 1. A method for condensing a functionalized allylic olefin substrate by metathesis chemistry, the method comprising the steps of:
(a) providing a functionalized allylic olefin substrate; (b) providing a ruthenium-based catalyst capable of catalyzing the metathesis condensation of the functionalized allylic olefin substrate; (c) contacting the functionalized allylic olefin substrate with the catalyst to form a reaction mixture; and (d) placing the reaction mixture under conditions that result in the formation of a functionalized olefin product via metathesis condensation, the functionalized olefin product having a different chemical structure than the functionalized allylic olefin substrate.
- 2. The method of claim 1, wherein the catalyst is 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene ruthenium benzylidene (Ru*).
- 3. The method of claim 2, wherein the functionalized allylic olefin substrate is functionalized with an electron rich functional group.
- 4. The method of claim 2, wherein the functionalized allylic olefin substrate is selected from the group consisting of allyl alcohol and allyl cyanide.
- 5. The method of claim 4, wherein the functionalized allylic olefin substrate is allyl alcohol and the functionalized allylic olefin product is 2-butene-1,4-diol.
- 6. The method of claim 4, wherein the functionalized allylic olefin substrate is allyl cyanide and the functionalized allylic olefin product is 1,4-dicyanobutene.
- 7. The method of claim 1, wherein the step (d) of placing the reaction mixture under conditions that result in the formation of the functionalized olefin product via metathesis condensation comprises placing the reaction mixture at a temperature of between about 10° C. and 70° C.
- 8. The method of claim 1, wherein the step (d) of placing the reaction mixture under conditions that result in the formation of the functionalized olefin product via metathesis condensation comprises placing the reaction mixture at a temperature of about 23° C. or less.
- 9. The method of claim 1, wherein the step (d) of placing the reaction mixture under conditions that result in the formation of the functionalized olefin product via metathesis condensation comprises placing the reaction mixture under about standard atmospheric pressure.
- 10. The method of claim 1, wherein the step (d) of placing the reaction mixture under conditions that result in the formation of the functionalized olefin product via metathesis condensation comprises applying a vacuum force to the reaction mixture.
- 11. The method of claim 1, wherein the step (d) of placing the reaction mixture under conditions that result in the formation of the functionalized olefin product via metathesis condensation comprises placing the reaction mixture under an inert atmosphere.
- 12. The method of claim 11, wherein the inert atmosphere is selected from N2 or Ar.
- 13. The method of claim 1, wherein the step (d) of placing the reaction mixture under conditions that result in the formation of the functionalized olefin product via metathesis condensation is performed under anhydrous conditions.
- 14. The method of claim 1, wherein substrate:catalyst ratio (mol:mol) is between about 1:1 to 1000:1.
- 15. The method of claim 1, wherein substrate:catalyst ratio (mol:mol) is greater than about 10:1.
- 16. The method of claim 1, further comprising a step (e) of hydrogenating the functionalized allylic olefin product.
- 17. The method of claim 16, wherein the step (e) of hydrogenating the functionalized allylic olefin product is catalyzed using residue of the ruthenium-based catalyst formed during the step (d) of placing the reaction mixture under conditions that result in the formation of a functionalized olefin product via metathesis condensation.
- 18. The method of claim 17, wherein the functionalized allylic olefin substrate is allyl alcohol, the functionalized allylic olefin product is 2-butene-1,4-diol, and the step (e) of hydrogenating the functionalized allylic olefin product results in the production of butane-1,4-diol.
- 19. A reaction mixture comprising a functionalized allylic olefin substrate; a ruthenium-based catalyst capable of catalyzing the metathesis condensation of the functionalized allylic olefin substrate; and a solvent, the solvent having dissolved therein the substrate and the catalyst.
- 20. The reaction mixture of claim 19, wherein the catalyst is 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene ruthenium benzylidene (Ru*).
- 21. The reaction mixture of claim 20, wherein the functionalized allylic olefin substrate is selected from the group consisting of allyl alcohol and allyl cyanide.
- 22. The reaction mixture of claim 21, wherein the functionalized allylic olefin substrate is allyl alcohol.
- 23. The reaction mixture of claim 21, wherein the functionalized allylic olefin substrate is allyl cyanide.
- 24. The method of claim 21, wherein the solvent is a hydrocarbon-based solvent.
- 25. The reaction mixture of claim 24, wherein the hydrocarbon-based solvent is selected from the group consisting of dichloromethane, tetrahydrofuran, dimethoxyethane, and acetone.
- 26. A reaction mixture comprising a functionalized allylic olefin substrate; a ruthenium-based catalyst capable of catalyzing the metathesis condensation of the functionalized allylic olefin substrate; a functionalized olefin product having a different chemical structure than the functionalized allylic olefin substrate, the product being formed by the metathesis condensation of the substrate; and a solvent, the solvent having dissolved therein the substrate and the catalyst.
- 27. The reaction mixture of claim 26, wherein the catalyst is 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene ruthenium benzylidene (Ru*).
- 28. The reaction mixture of claim 27, wherein the functionalized allylic olefin substrate is selected from the group consisting of allyl alcohol and allyl cyanide.
- 29. The reaction mixture of claim 28, wherein the functionalized allylic olefin substrate is allyl alcohol and the functionalized allylic olefin product is 2-butene-1,4-diol.
- 30. The reaction mixture of claim 28, wherein the functionalized allylic olefin substrate is allyl cyanide and the functionalized allylic olefin-product is 1,4-dicyanobutene.
CROSS REFERENCE TO RELATED APPLICATION
[0001] The present application claims the benefit of U.S. provisional patent application No. 60/201,918 filed May 4, 2000 and entitled “Metathesis Dimerization of Functionalized Allylic Olefins.”
STATEMENT AS TO FEDERALLY SPONSORED RESEARCH
[0002] This invention was made with United States Government support awarded by the Army Research Office, Grant No. DAAG55-97-1-0023; and by the National Science Foundation, Division of Materials Research, Grant No. DMR-9806492. The United States Government has certain rights in this invention.
Provisional Applications (1)
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Number |
Date |
Country |
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60201918 |
May 2000 |
US |