Claims
- 1. A method for synthesizing an olefin directly substituted with an electron-withdrawing group and substituted with at least one additional substituent, comprising contacting (a) a first olefinic reactant directly substituted with an electron-withdrawing group with (b) a second olefinic reactant substituted with a different substituent in the presence of (c) a catalyst composed of a Group 8 transition metal alkylidene complex under conditions and for a time period effective to allow cross-metathesis to occur, wherein the catalyst contains two anionic ligands, a carbene ligand, and one or two electron-donating heterocyclic ligands.
- 2. The method of claim 1, wherein the electron-withdrawing group is selected from halo, cyano, C1-C20 haloalkyl, C1-C20 alkylsulfonyl, C5-C24 arylsulfonyl, carboxyl, C5-C24 aryloxy, C1-C20 alkoxy, C6-C24 aryloxycarbonyl, C2-C20 alkoxycarbonyl, C6-C24 arylcarbonyl, C2-C20 alkylcarbonyl, formyl, nitro, quaternary amino, sulfhydryl, C1-C20 alkylthio, C5-C24 arylthio, hydroxyl, C5-C24 aryl, and C1-C20 alkyl, any of which may be substituted and/or heteroatom-containing.
- 3. The method of claim 2, wherein the electron-withdrawing group is selected from halo, cyano, C1-C12 haloalkyl, C1-C12 alkylsulfonyl, C5-C14 arylsulfonyl, carboxyl, C5-C14 aryloxy, C1-C12 alkoxy, C6-C14 aryloxycarbonyl, C2-C12 alkoxycarbonyl, C6-C14 arylcarbonyl, C2-C12 alkylcarbonyl, formyl, nitro, quaternary amino, sulfhydryl, C1-C12 alkylthio, C5-C24 arylthio, hydroxyl, C5-C24 aryl, and C1-C12 alkyl, any of which may be substituted and/or heteroatom-containing.
- 4. The method of claim 3, wherein the electron-withdrawing group is cyano.
- 5. The method of claim 1, wherein: the first olefinic reactant has the structure CH2═CER5 wherein E is the electron-withdrawing group and R5 is hydrogen or substituted and/or heteroatom-containing C1-C12 hydrocarbyl; and the second olefinic reactant has the structure
- 6. The method of claim 5, wherein R5, R8, and R10 are hydrogen.
- 7. The method of claim 6, wherein R9 is hydrogen.
- 8. The method of claim 7, wherein E is cyano, w is 1, J is C1-C6 alkylene, substituted C1-C6 alkylene, heteroatom-containing C1-C6 alkylene, and substituted heteroatom-containing C1-C6 alkylene, and R* is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups.
- 9. The method of claim 8, wherein J is C1-C6 alkylene and R* is selected from C1-C20 alkyl, substituted C1-C20 alkyl, C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, C5-C24 aryl, substituted C5-C24 aryl, C5-C24 heteroaryl, substituted C5-C24 heteroaryl, C6-C24 aralkyl, substituted C6-C24 aralkyl, C6-C24 heteroaralkyl, and substituted C6-C24 heteroaralkyl, hydroxyl, sulfhydryl, protected hydroxyl, protected sulfhydryl, C1-C20 alkoxy, C5-C24 aryloxy, C6-C24 aralkyloxy, C2-C20 alkylcarbonyl, C6-C24 arylcarbonyl, C2-C20 alkylcarbonyloxy, C6-C24 arylcarbonyloxy, C2-C20 alkoxycarbonyl, C6-C24 aryloxycarbonyl, halocarbonyl, C2-C20 alkylcarbonato, C6-C24 arylcarbonato, carboxy, carboxylato, carbamoyl, mono-(C1-C20 alkyl)-substituted carbamoyl, di-(C1-C20 alkyl)-substituted carbamoyl, di-N—(C1-C20 alkyl)-N—(C5-C24 aryl)-substituted carbamoyl, mono-(C5-C24 aryl)-substituted carbamoyl, di-(C6-C24 aryl)-substituted carbamoyl, thiocarbamoyl, mono-(C1-C20 alkyl)-substituted thiocarbamoyl, di-(C1-C20 alkyl)-substituted thiocarbamoyl, di-N—(C1-C20 alkyl)-N—(C6-C24 aryl)-substituted thiocarbamoyl, mono-(C6-C24 aryl)-substituted thiocarbamoyl, di-(C6-C24 aryl)-substituted thiocarbamoyl, carbamido, formyl, thioformyl, amino, mono-(C1-C20 alkyl)-substituted amino, di-(C1-C20alkyl)-substituted amino, mono-(C5-C24 aryl)-substituted amino, di-(C5-C24 aryl)-substituted amino, di-N—(C1-C20 alkyl)-N—(C1-C24 aryl)-substituted amino, C2-C20 alkylamido, C6-C24 arylamido, imino, C2-C20 alkylimino, C6-C24 arylimino, nitro, nitroso, sulfo, sulfonato, C1-C20 alkylthio, C5-C24 arylthio, C1-C20 alkylsulfinyl, C5-C24 arylsulfinyl, C1-C20 alkylsulfonyl, C5-C24 arylsulfonyl, boryl borono, boronato, phosphono, phosphonato, phosphinato, phospho, and phosphino.
- 10. The method of claim 8, wherein J is C1-C3 alkylene and R* is selected from hydroxyl, sulfhydryl, protected hydroxyl, protected sulfhydryl, C1-C12 alkoxy, C5-C14 aryloxy, C6-C14 aralkyloxy, C2-C12 alkylcarbonyl, C6-C14 arylcarbonyl, C2-C12 alkylcarbonyloxy, arylcarbonyloxy, C2-C12 alkoxycarbonyl, C6-C14 aryloxycarbonyl, halocarbonyl, di-(C1-C12 alkyl)-substituted carbamoyl, di-N—(C1-C12 alkyl)-N—(C5-C14 aryl)-substituted carbamoyl, mono-(C1-C14 aryl)-substituted carbamoyl, di-(C6-C14 aryl)-substituted carbamoyl, formyl, mono-(C1-C12 alkyl)-substituted amino, di-(C1-C12 alkyl)-substituted amino, mono-(C1-C14 aryl)-substituted amino, di-(C5-C14 aryl)-substituted amino, di-N—(C1-C20 alkyl)-N—(C1l-C24 aryl)-substituted amino, C2-C12 alkylamido, C6-C14arylamido, nitro, C1-C12 alkylthio, and C5-C14 arylthio.
- 11. The method of claim 10, wherein J is methylene and R* is selected from hydroxyl, protected hydroxyl, C1-C6 alkoxy, C5-C14 aryloxy, C6-C14 aralkyloxy, C2-C6 alkylcarbonyl, C6-C14 arylcarbonyl, halocarbonyl, formyl, di-(C1-C6 alkyl)-substituted amino, di-(C5-C14 aryl)-substituted amino, C1-C6 alkylthio, and C5-C14 arylthio.
- 12. The method of claim 5, wherein R5, R8, and R9 are hydrogen and R10 is -(J)w-R*.
- 13. The method of claim 12, wherein E is cyano, w is 1, J is C1-C6 alkylene, substituted C1-C6 alkylene, heteroatom-containing C1-C6 alkylene, or substituted heteroatom-containing C1-C6 alkylene, and R* is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups.
- 14. The method of claim 13, wherein J is C1-C6 alkylene and R* is selected from C1-C20 alkyl, substituted C1-C20 alkyl, C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, C5-C24 aryl, substituted C5-C24 aryl, C5-C24 heteroaryl, substituted C5-C24 heteroaryl, C6-C24 aralkyl, substituted C6-C24 aralkyl, C6-C24 heteroaralkyl, and substituted C6-C24 heteroaralkyl, hydroxyl, sulfhydryl, protected hydroxyl, protected sulfhydryl, C1-C20 alkoxy, C5-C24 aryloxy, C6-C24 aralkyloxy, C2-C20 alkylcarbonyl, C6-C24 arylcarbonyl, C2-C20 alkylcarbonyloxy, C6-C24 arylcarbonyloxy, C2-C20 alkoxycarbonyl, C6-C24 aryloxycarbonyl, halocarbonyl, C2-C20 alkylcarbonato, C6-C24 arylcarbonato, carboxy, carboxylato, carbamoyl, mono-(C1-C20 alkyl)-substituted carbamoyl, di-(C1-C20 alkyl)-substituted carbamoyl, di-N—(C1-C20 alkyl)-N—(C5-C24 aryl)-substituted carbamoyl, mono-(C5-C24 aryl)-substituted carbamoyl, di-(C6-C24 aryl)-substituted carbamoyl, thiocarbamoyl, mono-(C1-C20 alkyl)-substituted thiocarbamoyl, di-(C1-C20 alkyl)-substituted thiocarbamoyl, di-N—(C1-C20 alkyl)-N—(C6-C24 aryl)-substituted thiocarbamoyl, mono-(C6-C24 aryl)-substituted thiocarbamoyl, di-(C6-C24 aryl)-substituted thiocarbamoyl, carbamido, formyl, thioformyl, amino, mono-(C1-C20 alkyl)-substituted amino, di-(C1-C20alkyl)-substituted amino, mono-(C5-C24 aryl)-substituted amino, di-(C5-C24 aryl)-substituted amino, di-N—(C1-C20 alkyl)-N—(C5-C24 aryl)-substituted amino, C2-C20 alkylamido, C6-C24 arylamido, imino, C2-C20 alkylimino, C6-C24 arylimino, nitro, nitroso, sulfo, sulfonato, C1-C20 alkylthio, C5-C24 arylthio, C1-C20 alkylsulfinyl, C5-C24 arylsulfinyl, C1-C20 alkylsulfonyl, C5-C24 arylsulfonyl, boryl, borono, boronato, phosphono, phosphonato, phosphinato, phospho, and phosphino.
- 15. The method of claim 14, wherein J is C1-C3 alkylene and R* is selected from hydroxyl, sulfhydryl, protected hydroxyl, protected sulfhydryl, C1-C12 alkoxy, C5-C14 aryloxy, C6-C14 aralkyloxy, C2-C12 alkylcarbonyl, C6-C14 arylcarbonyl, C2-C12 alkylcarbonyloxy, arylcarbonyloxy, C2-C12 alkoxycarbonyl, C6-C14 aryloxycarbonyl, halocarbonyl, di-(C1-C12 alkyl)-substituted carbamoyl, di-N—(C1-C12 alkyl)-N—(C5-C14 aryl)-substituted carbamoyl, mono-(C5-C14 aryl)-substituted carbamoyl, di-(C6-C14 aryl)-substituted carbamoyl, formyl, mono-(C1-C12 alkyl)-substituted amino, di-(C1-C12 alkyl)-substituted amino, mono-(C5-C14aryl)-substituted amino, di-(C5-C14 aryl)-substituted amino, di-N—(C1-C20 alkyl)-N—(C5-C24 aryl)-substituted amino, C2-C12 alkylamido, C6-C14arylamido, nitro, C1-C12 alkylthio, and C5-C14 arylthio.
- 16. The method of claim 15, wherein J is methylene and R* is selected from hydroxyl, protected hydroxyl, C1-C6 alkoxy, C5-C14 aryloxy, C6-C14 aralkyloxy, C2-C6 alkylcarbonyl, C6-C14 arylcarbonyl, halocarbonyl, formyl, di-(C1-C6 alkyl)-substituted amino, di-(C5-C14 aryl)-substituted amino, C1-C6 alkylthio, and C5-C14 arylthio.
- 17. The method of claim 1, wherein the transition metal alkylidene complex has the structure of formula (VI)
- 18. The method of claim 17, wherein M is ruthenium, w, x, y, and z are zero, X and Y are N, and R3A and R4A are linked to form -Q-, such that the complex has the structure of formula (VIII)
- 19. The method of claim 18, wherein:
X1 and X2 are halo; Q is —CR11R12—CR13R14— or —CR11═CR13—, wherein R11, R12, R13, and R14 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, or wherein any two of R11, R12, R13, and R14 may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring; and R3 and R4 are aromatic.
- 20. The method of claim 19, wherein:
Q is —CR11R12—CR13R14— wherein R11, R12, R13, and R14 are independently selected from hydrogen, C1-C12 alkyl, substituted C1-C12 alkyl, C1-C12 heteroalkyl, substituted C1-C12 heteroalkyl, phenyl, and substituted phenyl; and R3 and R4 are unsubstituted phenyl or phenyl substituted with up to three substituents selected from C1-C20 alkyl, substituted C1-C20 alkyl, C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, C5-C24 aryl, substituted C5-C24 aryl, C5-C24 heteroaryl, C6-C24 aralkyl, C6-C24 alkaryl, or halide.
- 21. The method of claim 20, wherein R3 and R4 are mesityl, and R11, R12, R13, and R14 are hydrogen.
- 22. The method of claim 19, wherein one of R1 and R2 is hydrogen, and the other is selected from C1-C20 alkyl, C2-C20 alkenyl, and C5-C24 aryl, optionally substituted with one or more moieties selected from C1-C6 alkyl, C1-C6 alkoxy, and phenyl.
- 23. The method of claim 20, wherein one of R1 and R2 is hydrogen, and the other is selected from C2-C6 alkenyl and phenyl.
- 24. The method of claim 21, wherein R1 is hydrogen and R2 is phenyl.
- 25. The method of any one of claims 19, 20, 21, 22, 23, or 24, wherein L2 and L3 are selected from nitrogen-containing heterocycles, sulfur-containing heterocycles, and oxygen-containing heterocycles.
- 26. The method of claim 25, wherein L2 and L3 are nitrogen-containing heterocycles.
- 27. The method of claim 26, wherein L2 and L3 are selected from pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinnoline, quinazoline, naphthyridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine, purine, benzimidazole, bisimidazole, phenazine, acridine, carbazole, any of which is optionally substituted on a non-coordinating heteroatom with a nonhydrogen substituent.
- 28. The method of claim 27, wherein L2 and L3 are selected from pyridine and substituted pyridines.
- 29. The method of claim 28, wherein L2 and L3 are selected from pyridine, 3-halopyridine, 4-methylpyridine, and 4-phenylpyridine.
- 30. The method of any one of claims 19, 20, 21, 22, 23, or 24, wherein n is zero and L2 is selected from nitrogen-containing heterocycles, sulfur-containing heterocycles, and oxygen-containing heterocycles.
- 31. The method of claim 30, wherein L2 is a nitrogen-containing heterocycle.
- 32. The method of claim 31, wherein L2 is selected from pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinnoline, quinazoline, naphthyridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine, purine, benzimidazole, bisimidazole, phenazine, acridine, carbazole, any of which is optionally substituted on a non-coordinating heteroatom with a nonhydrogen substituent.
- 33. The method of claim 32, wherein L2 is selected from pyridine and substituted pyridines.
- 34. The method of claim 33, wherein L2 is selected from pyridine, 3-halopyridine, 4-methylpyridine, and 4-phenylpyridine.
- 35. The method of claim 1, wherein the catalyst has the structure of formula (II), (III), or (IV)
- 36. A method for synthesizing a substituted acrylonitrile, comprising contacting acrylonitrile with a substituted olefinic reactant in the presence of a catalyst composed of a Group 8 transition metal alkylidene complex under conditions and for a time period effective to allow cross-metathesis to occur, wherein the catalyst has the structure of formula (VIII)
- 37. The method of claim 36, wherein R11, R12, R13, and R14 are hydrogen, and R3 and R4 are mesityl.
- 38. The method of claim 36, wherein the substituted olefinic reactant has the structure CH2═CH(CH2—R*) or CH(CH2—R*)═CH(CH2—R*) wherein R* is selected from hydroxyl, protected hydroxyl, C1-C6 alkoxy, C5-C14 aryloxy, C6-C14 aralkyloxy, C2-C6 alkylcarbonyl, C6-C14 arylcarbonyl, halocarbonyl, formyl, di-(C1-C6 alkyl)-substituted amino, di-(C5-C14 aryl)-substituted amino, C1-C6 alkylthio, and C5-C14 arylthio.
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. § 119(e)(1) to provisional U.S. patent application Serial No. 60/370,308, filed Apr. 5, 2002, the disclosure of which is incorporated by reference in its entirety.
Provisional Applications (1)
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Number |
Date |
Country |
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60370308 |
Apr 2002 |
US |