Method for preparation of ruthenium-based metathesis catalysts with chelating alkylidene ligands

Patent metadata

Field	Value
Publication number	US-9562116-B2
Application number	US-201414472088-A
Country	US
Kind code	B2
Filing date	Aug 28, 2014
Priority date	May 7, 2009
Publication date	Feb 7, 2017
Grant date	Feb 7, 2017

Abstract

The invention relates to a method for preparation of ruthenium-based carbene catalysts with a chelating alkylidene ligand (“Hoveyda-type catalysts”) by reacting a penta coordinated ruthenium (II)-alkylidene complex of the type (L) (Py)X1X2Ru(alkylidene) with a suitable olefin derivative in a cross metathesis reaction. The method delivers high yields and is conducted preferably in aromatic hydrocarbon solvents. The use of phosphine-containing Ru carbene complexes as starting materials can be avoided. Catalyst products with high purity, particularly with low Cu content, can be obtained.

First claim

The invention claimed is:

1. Method for the preparation of a ruthenium-based carbene catalyst with a chelating alkylidene ligand comprising the reaction of a ruthenium (II)-alkylidene complex with an olefin derivative according to the equation:

wherein
L is a substituted or unsubstituted imidazole or imidazolidine ring,
X 1 and X 2 are, independently from each other, inorganic or organic anionic ligands selected from halide anions, pseudohalide anions, hydroxides, acetates, trifluoracetates or carboxylates,
Y 1 and Y 2 are, independently from each other, hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 6 -alkylthio, aryl, arylthio, C 1 -C 6 -alkylsulfonyl or C 1 -C 6 -alkylsulfinyl, or Y 1 and Y 2 are taken together to form a ring of the indenylidene type according to the formula

wherein in said formula R 3 is hydrogen or a substituted or unsubstituted aryl group,
Py is an N-heterocyclic two-electron donor ligand selected from the group consisting of pyridine, 3-bromo-pyridine, 4-methyl-pyridine, quinolone, and piperidine,
R 0 and R 1 are, independently from each other, hydrogen, C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -alkynyl, or a substituted or unsubstituted aryl group,
a, b, c and d are, independently from each other, hydrogen, C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -alkynyl, or aryl group, or an electron withdrawing group (“EWG”), with the provision that two of a, b, c or d can form a ring,
Z is a heterodonor atom selected from the group consisting of oxygen (O), sulphur (S), and nitrogen (N), or a group comprising a heterodonor atom,
R 2 is a substituted or unsubstituted hydrocarbon group selected from alkyl, alkenyl, alkynyl, aryl, alkylamino, alkylthio, a hydrocarbon containing a substituted or unsubstituted keto group, a hydrocarbon containing a substituted or unsubstituted ester group and wherein R 2 and/or Z may form a quinolone, a quinoxaline, or an indol ring system with d.

2. The method according to claim 1 , wherein
L is a saturated H 2 IMes (=1, 3-dimesityl-imidazolidine-2-ylidene) or unsaturated IMes (=1, 3-dimesityl-imidazole-2-ylidene) ligand,
X 1 and X 2 are, independently from each other, anionic ligands selected from the group consisting of Cl—, Br—, and I—,
Y 1 and Y 2 form a ring of the indenylidene type according to the formula

wherein R 3 is a substituted or unsubstituted phenyl group,
Py is a substituted or un-substituted pyridine ligand
R 0 and R 1 are, independently from each other, hydrogen or a C 1 -C 10 -alkyl group,
a, b, c and d are, independently from each other, hydrogen, C 1 -C 10 -alkyl, a phenyl, an aryl group or an electron withdrawing group (EWG) selected from the group consisting of F, Cl, Br, I, —CF 3 , —NO 2 , —N(H)—CO—CH 3 , —N(alkyl)-CO—CH 3 , —N(H)—CO—CF 3 ; —N(alkyl)-CO—CF 3 , —O 2 S-(alkyl), —O—CO-(alkyl), and —SO 2 —N(CH 3 ) 2 ,
Z is a heterodonor atom selected from oxygen (O) or nitrogen (N),
R 2 is a substituted or unsubstituted alkyl group selected from —CH 3 or —CH(CH 3 ) 2 , a substituted or unsubstituted keto group selected from —CH 2 —CO—CH 3 , —CH 2 —CO—C 2 H 5 , —CH(CH 3 )—CO—CH 3 , or —CH(CH 3 )—CO—C 2 H 5 , a substituted or unsubstituted ester group selected from —CH 2 —CO—CH 3 , —CH 2 —CO—O—C 2 H 5 , —CH(CH 3 )—CO—CH 3 , or —CH(CH 3 )—CO—O—C 2 H 5 , or —CH(CH 3 )—CO—O—C 2 H 4 —N(CH 3 ) 2 , and
wherein R 2 and/or the heterodonor atom Z may form a quinolone, a quinoxaline, or an indol ring system with d.

3. The method according to claim 1 , wherein the reaction is a cross metathesis reaction (CM).

4. The method according to claim 1 , wherein the reaction is conducted in aromatic hydrocarbon solvents.

5. The method according to claim 1 , wherein the reaction temperature is in the range of 20 to 100° C.

6. The method according to claim 1 , wherein the molar ratio of olefinic derivative vs. ruthenium (II)-alkylidene complex is in the range of 2:1.

7. The method according to claim 1 , wherein the reaction time is in the range of 1 to 8 hours.

8. The method according to claim 1 , wherein the olefin derivative is selected from (E/Z)-1-Isopropoxy-2-(1-propenyl)-benzene, (E/Z)-1-[2-(1-propen-1-yl)-phenoxy]-2-propanone), 2-isopropoxy-4-nitro-styrene, 8-vinylquinolin or 2-isopropoxy-3-vinyl-biphenyl.

9. The method according to claim 1 , further comprising the separation of the ruthenium-based carbene catalyst with a chelating alkylidene ligand from the reaction mixture by precipitation and filtration.

10. Ruthenium-based carbene catalyst with a chelating alkylidene ligand, obtained by the method according to claim 1 , wherein the Cu content is <10 ppm (as determined by ICP),
wherein, when Z is nitrogen (N), R 2 is an unsubstituted hydrocarbon group selected from alkyl, alkenyl, alkynyl, aryl, alkylamino, alkylthio, a hydrocarbon containing a substituted or unsubstituted keto group, or a hydrocarbon containing a substituted or unsubstituted ester group, and R 2 and/or Z may form a quinolone, a quinoxaline, or an indol ring system with d, and
wherein, when Z is oxygen (O), R 2 is an unsubstituted hydrocarbon group selected from alkenyl, alkynyl, aryl, alkylamino, or alkylthio.

11. The method of claim 1 , wherein Z is a group comprising sulfinyl (>S═O).

12. The method of claim 1 , wherein R 2 is —C(R a ) 2 —CO—C(R b ) 3 , wherein in said groups R a is hydrogen or C 1 -C 10 -alkyl, and R b is hydrogen, C 1 -C 10 -alkyl, C 1 -C 10 -fluoroalkyl, C 1 -C 10 -alkylamino, C 1 -C 10 -alkyl ammonium or C 2 -C 10 -alkenyl.

13. The method of claim 1 , wherein R 2 is —C(R a ) 2 —CO—O(R c ), wherein in said groups R a is hydrogen or C 1 -C 10 -alkyl, and R c is C 1 -C 10 -alkyl, C 1 -C 10 -fluoroalkyl, C 1 -C 10 -alkylamino, C 1 -C 10 -alkyl ammonium or C 2 -C 10 -alkenyl.

14. The method of claim 6 , wherein the molar ratio of olefinic derivative vs. ruthenium (II)-alkylidene complex is in the range of 1.1:1.

15. The method of claim 7 , wherein the reaction time is in the range of 1 to 4 hours.

16. The method of claim 1 , wherein the substituted or unsubstituted aryl is phenyl.

Assignees

• Umicore Ag & Co Kg
• Graz Univ Of Tech

Inventors

• Winde Roland
• Doppiu Angelino
• Woerner Eileen
• Rivas-Nass Andreas
• Karch Ralf
• Slugovc Christian
• Schinagl Christina

Classifications

• C07F15/0046 Primary

  Ruthenium compounds · CPC title

• B01J31/2265

  Carbenes or carbynes, i.e.(image) · CPC title

• B01J2231/543

  alkene metathesis · CPC title

• B01J31/2278

  Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts · CPC title

• C08F4/80 Primary

  selected from iron group metals or platinum group metals · CPC title