Chelating carbene ligand precursors and their use in the synthesis of metathesis catalysts

• US 7,820,843 B2
• Filed: 12/11/2008
• Issued: 10/26/2010
• Est. Priority Date: 11/15/2001
• Status: Expired due to Term

• Current Assignee: Umicore AG & Company KG (Umicore S.A.)
• Original Assignee: Materia Incorporated (Exxon Mobil Corporation)
• Inventors: Schrodi, Yann, Woertink, Jason K., Gindelberger, David E., Haar, Christopher M., Pederson, Richard L.
• Primary Examiner(s): NAZARIO GONZALEZ, PORFIRIO
• Application Number:
  US12/333,125
• Publication Number:
  US 20090088581A1
• Time in Patent Office: 684 Days
• Field of Search: 556/136, 556/22, 549/3, 549/209, 546/4, 546/103, 544/181
• US Class Current: 556/22
• CPC Class Codes: B01J 2231/50 Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
• CPC Class Codes: B01J 2231/54 Metathesis reactions, e.g. olefin metathesis
• CPC Class Codes: B01J 2231/543 alkene metathesis
• CPC Class Codes: B01J 2531/821 Ruthenium
• CPC Class Codes: B01J 2531/825 Osmium
• CPC Class Codes: B01J 31/1805 the ligands containing nitrogen
• CPC Class Codes: B01J 31/2204 the ligands containing oxygen or sulfur as complexing atoms
• CPC Class Codes: B01J 31/2208 Oxygen, e.g. acetylacetonates
• CPC Class Codes: B01J 31/2265 Carbenes or carbynes, i.e.(image)
• CPC Class Codes: B01J 31/2273 with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
• CPC Class Codes: B01J 31/2278 Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
• CPC Class Codes: B01J 31/2404 Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
• CPC Class Codes: B01J 31/2414 comprising aliphatic or saturated rings
• CPC Class Codes: C07F 15/002 Osmium compounds
• CPC Class Codes: C07F 15/0046 Ruthenium compounds

Abstract

Chelating ligand precursors for the preparation of olefin methathesis catalysts are disclosed. The resulting catalysts are air stable monomeric species capable of promoting various methathesis reactions efficiently, which can be recovered from the reaction mixture and reused. Internal olefin compounds, specifically beta-substituted styrenes, are used as ligand precursors. Compared to terminal olefin compounds such as unsubstituted styrenes, the beta-substituted styrenes are easier and less costly to prepare, and more stable since they are less prone to spontaneous polymerization. Methods of preparing chelating-carbene methathesis catalysts without the use of CuCl are disclosed. This eliminates the need for CuCl by replacing it with organic acids, mineral acids, mild oxidants or even water, resulting in high yields of Hoveyda-type methathesis catalysts. The invention provides an efficient method for preparing chelating-carbene metathesis catalysts by reacting a suitable ruthenium complex in high concentrations of the ligand precursors followed by crystallization from an organic solvent.

Claims

1. A chelating carbene complex of the formula:

2. The chelating carbene complex of claim 1, wherein the chelating carbene complex is prepared by a method comprising contacting a metathesis-active metal carbene complex with a beta-substituted styrene ligand precursor, wherein the metathesis-active metal carbene complex is of the formula X¹X²L¹L²M=CR¹R², wherein

X¹, X², L¹, and M are as defined in claim 1;

L² is any neutral electron donor, and wherein any of two or three of X¹, X², L¹, and L² may form a multidentate ligand; and

R¹ and R² are each independently, selected from hydrogen or a substituent selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, alkylcarboxylate, arylcarboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkylsulfinyl, or trialkylsilyl, wherein each of the substituents is substituted or unsubstituted, and wherein R¹ and R² may be linked to form a substituted or unsubstituted cyclic group.

3. The chelating carbene complex of claim 2, wherein the ligand precursor is of the formula

4. The chelating carbene complex of claim 1, wherein L¹ is a phosphine or a heterocyclic carbene ligand.

5. The chelating carbene complex of claim 1, wherein Z is selected from the group consisting of hydrogen, aryl, functionalized alkyl, and functionalized aryl where the functional group(s) may be independently one or more or the following:

alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, and borate.

6. The chelating carbene complex of claim 1, wherein the functional groups of Z may be independently one or more or the following:

halogen, nitrate, isocyanate, hydroxyl, ether, amine, imine, amide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, and borate.

7. The chelating carbene complex of claim 1, wherein Y is oxygen and at least one of R⁵, R⁶, R⁷, and R⁸ is heteroaryl, carbonyl, nitrile, nitro, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate.

8. The chelating carbene complex of claim 1, wherein Y is oxygen and at least one of R⁵, R⁶, R⁷, and R⁸ is alkyl, aryl, functionalized alkyl, or functionalized aryl, and at least one of R⁵, R⁶, R⁷, and R⁸ is heteroaryl, carbonyl, nitrile, nitro, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate.

9. The chelating carbene complex of claim 1, wherein at least one of R⁵, R⁶, R⁷, and R⁸ is alkyl, aryl, or an alkyl or alkoxy functionalized alkyl or functionalized aryl, and at least one of R⁵, R⁶, R⁷, and R⁸ is heteroaryl, carbonyl, nitrile, nitro, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, and borate.

10. A chelating carbene complex of the formula:

11. The chelating carbene complex of claim 10, wherein L¹ is a phosphine or a heterocyclic carbene ligand.

12. The chelating carbene complex of claim 10, wherein Z is selected from the group consisting of hydrogen, sec-butyl, t-butyl, neopentyl, aryl, functionalized alkyl, and functionalized aryl where the functional group(s) may independently be or more or the following:

alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, and borate.

13. The chelating carbene complex of claim 10, wherein the functional groups of Z may be independently one or more or the following:

halogen, nitrate, isocyanate, hydroxyl, ether, amine, imine, amide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, and borate.

14. The chelating carbene complex of claim 10, wherein Y is oxygen and at least one of R⁵, R⁶, R⁷, and R⁸ is heteroaryl, carbonyl, nitrile, nitro, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate.

15. The chelating carbene complex of claim 10, wherein Y is oxygen and at least one of R⁵, R⁶, R⁷, and R⁸ is alkyl, aryl, functionalized alkyl, or functionalized aryl, and at least one of R⁵, R⁶, R⁷, and R⁸ is heteroaryl, carbonyl, nitrile, nitro, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate.

16. The chelating carbene complex of claim 10, wherein at least one of R⁵, R⁶, R⁷, and R⁸ is alkyl, aryl, or an alkyl or alkoxy functionalized alkyl or functionalized aryl, and at least one of R⁵, R⁶, R⁷, and R⁸ is heteroaryl, carbonyl, nitrile, nitro, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, and borate.

17. A chelating carbene complex of the formula:

18. The chelating carbene complex of claim 17, wherein L¹ is a phosphine ligand.

19. The chelating carbene complex of claim 17, wherein Z is selected from the group consisting of hydrogen, sec-butyl, t-butyl, neopentyl, aryl, functionalized alkyl, and functionalized aryl where the functional group(s) may independently be or more or the following:

alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, and borate.

20. The chelating carbene complex of claim 17, wherein the functional groups of Z may be independently one or more or the following:

halogen, nitrate, isocyanate, hydroxyl, ether, amine, imine, amide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, and borate.

21. The chelating carbene complex of claim 17, wherein Y is oxygen and at least one of R⁵, R⁶, R⁷, and R⁸ is heteroaryl, carbonyl, nitrile, nitro, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate.

22. The chelating carbene complex of claim 17, wherein Y is oxygen and at least one of R⁵, R⁶, R⁷, and R⁸ is alkyl, aryl, functionalized alkyl, or functionalized aryl, and at least one of R⁵, R⁶, R⁷, and R⁸ is heteroaryl, carbonyl, nitrile, nitro, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate.

23. The chelating carbene complex of claim 22, wherein at least one of R⁵, R⁶, R⁷, and R⁸ is alkyl, aryl, or an alkyl or alkoxy functionalized alkyl or functionalized aryl, and at least one of R⁵, R⁶, R⁷, and R⁸ is heteroaryl, carbonyl, nitrile, nitro, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, and borate.