Claims
- 1. A compound having the structure of formula (IIA) or (IIB)
- 2. The compound of claim 1, having the structure of formula (IIA).
- 3. The compound of claim 1, having the structure of formula (IIB).
- 4. The compound of claim 1, wherein:
R1 is C1-C12 hydrocarbyl; and R2 and R5 are independently selected from the group consisting of C5-C30 aryl, substituted C5-C30 aryl, C5-C30 heteroaryl, and substituted C5-C30 heteroaryl; and R3 and R4 are hydrogen.
- 5. The compound of claim 4, wherein:
R1 is C1-C6 alkyl; and R2 and R5 are independently selected from monocyclic aryl and heteroaryl, and are optionally substituted with 1 to 4 substituents selected from the group consisting of halo, hydroxyl, and C1-C12 hydrocarbyl.
- 6. The compound of claim 5, wherein:
R1 is C1-C3 alkyl; R2 is selected from phenyl, phenyl substituted with 1 or 2 substituents selected from the group consisting of halo, hydroxyl, and C1-C6 alkyl, and five-membered and six-membered heteroaryl rings optionally substituted with a C1-C12 hydrocarbyl group; and R5 is selected from phenyl and phenyl substituted with 1 or 2 substituents selected from the group consisting of halo, hydroxyl, and C1-C6 alkyl.
- 7. The compound of claim 6, wherein:
R1 is methyl; R2 is phenyl or 5-methylfuryl; and R5 is phenyl.
- 8. The compound of claim 7, wherein R2 is 5-methylfuryl.
- 9. The compound of claim 1, in the form of an acid addition salt composed of compound (IIA) or (II B) and a Bronsted acid.
- 10. The compound of claim 9, wherein the Bronsted acid is selected from the group consisting of acids having a pKa less than about 5 and combinations thereof.
- 11. The compound of claim 10, wherein the Bronsted acid is an inorganic acid.
- 12. The compound of claim 11, wherein the Bronsted acid is selected from the group consisting of hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, perchloric acid, phosphoric acid, chromic acid, and combinations thereof.
- 13. The compound of claim 10, wherein the Bronsted acid is an organic acid.
- 14. The compound of claim 13, wherein the organic acid is selected from the group consisting of, carboxylic acids, sulfonic acids, phosphonic acids, and phenols substituted with 1 to 5 electron-withdrawing substituents.
- 15. The compound of claim 13, wherein the organic acid is selected from the group consisting of acetic acid, propionic acid, glycolic acid, pyruvic acid, oxalic acid, malic acid, malonic acid, succinic acid, maleic acid, fumaric acid, tartaric acid, citric acid, benzoic acid, 2-nitrobenzoic acid, cinnamic acid, mandelic acid, methanesulfonic acid, ethanesulfonic acid, triflic acid, p-toluenesulfonic acid, salicylic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, and combinations thereof.
- 16. The compound of claim 1, wherein the compound is covalently bound, directly or indirectly, to a solid support.
- 17. A process for catalyzing a reaction between an α,β-unsaturated ketone and a second reactant by lowering the energy level of the lowest unoccupied molecular orbital (LUMO) of the ketone, comprising:
contacting an α,β-unsaturated ketone with the second reactant in the presence of an imidazolidinone catalyst and an acid, wherein the catalyst has the structure of formula (IIA) or (IIB) 32in which R1 is selected from the group consisting of C1-C12 hydrocarbyl, substituted C1-C12 hydrocarbyl, heteroatom-containing C1-C12 hydrocarbyl, and substituted heteroatom-containing C1-C12 hydrocarbyl, R2 and R5 are independently selected from cyclic groups optionally substituted with 1 to 4 non-hydrogen substituents and containing zero to 3 heteroatoms, and R3 and R4 are independently selected from the group consisting of hydrogen, halo, hydroxyl, C1-C12 hydrocarbyl, substituted C1-C12 hydrocarbyl, heteroatom-containing C1-C12 hydrocarbyl, and substituted heteroatom-containing C1-C12 hydrocarbyl, and further wherein the second reactant is capable of reacting with the ketone by virtue of the lowered LUMO of the aldehyde in the presence of the catalyst.
- 18. The process of claim 17, wherein the α,β-unsaturated ketone has the structure of formula (III)
- 19. The process of claim 18, wherein:
R6, R7, and R8 are independently selected from the group consisting of hydrogen, C1-C24 alkyl, C2-C24 alkenyl, C2-C24 alkynyl, C1-C24 alkoxy, C2-C24 alkenyloxy, C2-C24 alkynyloxy, C5-C30 aryl, C5-C30 aryloxy, C2-C24 alkoxyalkyl, C6-C30 aryloxyalkyl, hydroxyl, sulfhydryl, C2-C24 alkylcarbonyl, C6-C30 arylcarbonyl, C2-C24 alkoxycarbonyl, C6-C30 aryloxycarbonyl, halocarbonyl, C2-C24 alkylcarbonato, C6-C30 arylcarbonato, carboxy, carboxylato, carbamoyl, mono- and di-(C1-C24 alkyl)-substituted carbamoyl, mono- and di-(C5-C20 aryl)-substituted carbamoyl, amino, mono- and di-(C1-C24 alkyl)-substituted amino, mono- and di-(C5-C20 aryl)-substituted amino, C2-C24 alkylamido, C6-C30 arylamido, imino, C2-C24 alkylimino, C6-C30 arylimino, nitro, nitroso, sulfo, sulfonato, C1-C24 alkylsulfanyl, C5-C30 arylsulfanyl, C1-C24 alkylsulfinyl, C5-C30 arylsulfinyl, C1-C24 alkylsulfonyl, C5-C30 arylsulfonyl, phosphono, phosphonato, phosphinato, phospho, phosphino, and combinations thereof, and further wherein any two of R6, R7, and R8 taken together can form a cyclic structure selected from five-membered rings, six-membered rings, and fused five-membered and/or six-membered rings, wherein the cyclic structure is aromatic, alicyclic, heteroaromatic, or heteroalicyclic, and has zero to 4 non-hydrogen substituents and zero to 3 heteroatoms; and R10 is hydrogen, C1-C6 alkyl, or substituted C1-C6 alkyl R10 is hydrogen, C1-C6 alkyl, or substituted C1-C6 alkyl.
- 20. The process of claim 19, wherein R6 and R8 are hydrogen.
- 21. The process of claim 20, wherein R7 is selected from the group consisting of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C5-C20 aryl, C2-C12 alkoxyalkyl, and C6-C20 aryloxyalkyl.
- 22. The process of claim 21, wherein R7 is selected from the group consisting of hydrogen, C1-C6 alkyl, C5-C12 aryl, and C6-C12 aryloxyalkyl, and R10 is hydrogen, methyl, ethyl, or n-propyl.
- 23. The process of claim 18, wherein the second reactant is directly or indirectly bound to the ketone, such that the reaction is intramolecular.
- 24. The process of claim 18, wherein the reaction is selected from the group consisting of cycloaddition reactions, 1,4 nucleophilic conjugate addition reactions, 1,4 radical addition reactions, organometallic insertions reactions, ene reactions, and any combination thereof occurring in tandem.
- 25. The process of claim 24, wherein the reaction is a cycloaddition reaction.
- 26. The process of claim 25, wherein the cycloaddition reaction is a [2+2] cycloaddition reaction, a [3+2] cycloaddition reaction, or a [4+2] cycloaddition reaction.
- 27. The process of claim 26, wherein the cycloaddition reaction is a [4+2] cycloaddition reaction.
- 28. The process of claim 27, wherein the second reactant is a 1,3-diene and the [4+2] cycloaddition reaction is a Diels-Alder reaction.
- 29. The process of claim 28, wherein the second reactant is a nucleophile containing a pi bond, a lone pair-bearing heteroatom, or a negative charge.
- 30. The process of claim 29, wherein the second reactant is an aromatic or heteroaromatic compound, and the reaction is an alkylation reaction.
- 31. The process of claim 30, wherein the second reactant has the structure of formula
- 32. The process of claim 31, wherein:
Q is phenyl substituted with zero to 2 nonhydrogen substituents selected from the group consisting of C1-C12 alkyl, C1-C12 alkoxy, and halo; R11 is selected from the group consisting of hydrogen, C1-C12 alkyl, C1-C12 alkenyl, C5-C20 aryl, and C5-C20 aralkyl; and X is CR12.
- 33. The process of claim 32, wherein R12 is -L1-Nu: wherein L1 is a hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene linker with 2 to 6 atoms in the linker backbone, and Nu: is a nucleophilic group capable of addition to an unsaturated bond.
- 34. The process of claim 33, wherein Nu: is selected from the group consisting of secondary amino, hydroxyl, and sulfhydryl.
- 35. A process for catalyzing a reaction between an α,β-unsaturated ketone and a second reactant by lowering the energy level of the lowest unoccupied molecular orbital (LUMO) of the ketone, comprising: contacting an α,β-unsaturated ketone with the second reactant in the presence of the catalyst of claim 9, wherein the second reactant is capable of reacting with the ketone by virtue of the lowered LUMO of the aldehyde in the presence of the catalyst.
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. §119(e)(1) to provisional U.S. patent application Ser. No. 60/338,384, filed Dec. 5, 2001. The disclosure of the aforementioned application is incorporated by reference in its entirety.
Provisional Applications (1)
|
Number |
Date |
Country |
|
60338384 |
Dec 2001 |
US |