# US 11,999,754 B2 · Ruthenium complexes and their use in olefin metathesis reactions

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- Number: US 11,999,754 B2
- Document ID: US11999754B2
- Status: Granted
- Kind: B2
- Application number: 17/048,092
- Filed: 2019-04-16
- Published: 2021-04-08
- Granted: 2024-06-04
- Earliest claimed: 2018-04-16
- Assignees: Apeiron Synthesis S.A.
- Applicants: Apeiron Synthesis S.A.
- Inventors: Rafal Gawin; Patryk Krajczy; Anna Gawin; Krzysztof Skowerski
- Web page: https://patentgrep.com/patent/US11999754B2

## CPC

- B01J 31/2278: {Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts}
- C07F 15/0046: {Ruthenium compounds}
- B01J 31/1805: {the ligands containing nitrogen}
- B01J 31/1825: {Ligands comprising condensed ring systems, e.g. acridine, carbazole}
- C07C 6/04: at a carbon-to-carbon double bond
- B01J 2231/543: alkene metathesis
- B01J 2531/821: Ruthenium
- C07C 2531/22: Organic complexes
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

The invention relates to a ruthenium complex of formula (1), (1) wherein all variables have a meaning as defined in the specification to be used as a (pre)catalyst in the olefin metathesis reaction, ring metathesis reaction (RCM), homometathesis (self-CM), cross-metathesis including ethanolysis (CM).

## Claims

### Claim 1

A ruthenium complex of formula 1
wherein:
X1, X2 are each independently an anionic ligand selected from such as halogen atom, —OR, —SR, —C(C═O)R, where R is C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, which are optionally substituted with at least one C1-C12 alkyl, optionally C1-C12 perhalogenalkyl, optionally C1-C12 alkoxy, optionally a halogen atom;
R1 is a hydrogen atom or C5-C24 aryl, C1-C25 alkyl, C5-C25 heteroaryl, C7-C24 aralkyl, which are optionally substituted by at least one C1-C12 alkyl, optionally C1-C12 perhalogenalkyl, optionally C1-C12 alkoxy, optionally a halogen atom, wherein the alkyl groups may be interconnected to form a ring;
R2 is C5-C24 aryl, C5-C25 heteroaryl, C7-C24 aralkyl, which are optionally substituted by at least one C1-C12 alkyl, optionally C1-C12 perhalogenalkyl, optionally C1-C12 alkoxy, optionally a halogen atom, wherein the alkyl groups may be interconnected to form a ring;
R3 is C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl, or C5-C20 heteroaryl, which is optionally substituted by at least one C1-C12 alkyl, C1-C12 perhalogenalkyl, C2-C12 alkoxy or a halogen atom;
R4, R5, R6, R7, R8, R9 are each independently a hydrogen atom, C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl, or C5-C20 heteroaryl, which is optionally substituted by at least one C1-C12 alkyl, C1-C12 perhalogenalkyl, C1-C12 alkoxy or a halogen atom, and the R4 and R5 and/or R8 and R9 groups may optionally be interconnected to form a cyclic system C4-C10; and
a, b, c, d—are each independently a hydrogen atom, a halogen atom, C1-C25 alkyl, C1-C25 perfluoroalkyl, C3-C7 cycloalkyl, C1-C25 alkoxy, C5-C24 aryl, C7-C24 aralkyl, C5-C25 heteroaryl, 3-12-membered heterocycle, wherein the alkyl groups may be interconnected to form a ring; also, each of them can be independently an ether (—OR′), thioether (—SR′), nitro (—NO2), cyano (—CN), amide (—CONR′R″), carboxy and ester (—COOR′), sulfa (—SO2R′), sulfonamide (SO2NR′R″), formyl and ketone (—COR′) group, in which groups R′ and R″ are each C1-C25 alkyl, C1-C25 perfluoroalkyl, C5-C24 aryl, C5-C25 heteroaryl, C5-C24 perfluoroaryl.

### Claim 2 (depends on 1)

The complex according to claim 1, characterised in that:
X1 and X2 are halogen atoms;
R3 is aryl, which is optionally substituted by at least one C1-C12 alkyl, C1-C12 perhalogenalkyl, C2-C12 alkoxy or a halogen atom;
R4, R5, R8, R9 are each independently a hydrogen atom, C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl, or C5-C20 heteroaryl, which is optionally substituted by at least one C1-C12 alkyl, C1-C12 perhalogenalkyl, C1-C12 alkoxy or a halogen atom, and the R4 and R5 and/or the R8 and R9, groups may optionally be interconnected to form a cyclic system C4-C10;
R6, R7 are hydrogen atoms; and
a, b, c, d—are each independently a halogen atom, an ether (—OR′), thioether (—SR′), nitro (—NO2), cyano (—CN), amide (—CONR′R″), carboxy and ester (—COOR′), sulfa (—SO2R′), sulfonamide (—SO2NR′R″), formyl and ketone (—COR′) group, in which groups R′ and R″ are each independently C1-C25 alkyl, C1-C25 perfluoroalkyl, C5-C24 aryl, C5-C25 heteroaryl, C5-C24 perfluoroaryl.

### Claim 3 (depends on 1)

The complex according to claim 1, characterised in that:
X1 and X2 are halogen atoms;
R3 is aryl, which is optionally substituted by at least one C1-C12 alkyl, C1-C12 perhalogenalkyl, C2-C12 alkoxy or a halogen atom;
R4, R5, R8, R9 are each independently a hydrogen atom, C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl, which is optionally substituted by at least one C1-C12 alkyl, and R4 and R5 and/or the R8 and R9, groups may optionally be interconnected to form a cyclic system C4-C10;
R6, R7 are hydrogen atoms; and
a, b, c, d—are each independently a halogen atom, an ether (—OR′), nitro (—NO2), amide (—CONR′R″), ester (—COOR′), sulfa (—SO2R′), sulfonamide (—SO2NR′R″) group, in which groups R′ and R″ are each C1-C25 alkyl, C5-C24 aryl.

### Claim 4 (depends on 1)

The complex according to claim 1, characterised in that:
X1 and X2 are chlorine atoms;
R3 is aryl, which is optionally substituted by at least one C1-C12 alkyl;
R4, R5 are each independently C1-C12 alkyl, C5-C20 aryl, which is optionally substituted by at least one C1-C12 alkyl, and the R4 and R5 groups may optionally be interconnected to form a cyclic system C4-C10;
R6, R7 are hydrogen atoms;
R8, R9 are each independently C1-C12 alkyl; and
a, b, c, d—are each independently a halogen atom, an ether (—OR′) group, in which group R′ denotes as follows: C1-C25 alkyl.

### Claim 5 (depends on 1)

The complex according to claim 1, characterised in that:
X1 and X2 are chlorine atoms;
R3 is aryl, which is optionally substituted by at least one C1-C12 alkyl;
R4, R5 are each independently C1-C12 alkyl, C5-C20 aryl, and the R4 and R5 groups may optionally be interconnected to form a cyclic system C4-C10;
R6, R7 are hydrogen atoms;
R8, R9 are each independently methyl groups; and
a, b, c, d—are each a hydrogen atom or a metoxy (—OMe) group.

### Claim 6 (depends on 1)

The complex according to claim 1 with a structure represented by a structural formula select from formulas 1a-1j:

### Claim 7 (depends on 1)

A method comprising:
adding the ruthenium complex according to claim 1 as a (pre)catalyst to a solution to produce an olefin metathesis reaction.

### Claim 8 (depends on 1, 7)

The method of claim 7, wherein the adding step is accomplished by using the ruthenium complex according to claim 1 as a (pre)catalyst for a ring metathesis reaction (RCM), homometathesis (self-CM), or cross-metathesis, including ethenolysis (CM).

### Claim 9 (depends on 7)

The method of claim 7 wherein the adding step is accomplished by using a solution that is an organic solvent such as toluene, benzene, mesitylene, dichloromethane, ethyl acetate, methyl acetate, tertbutyl methyl ether, or cyclopentylmethyl ether.

### Claim 10 (depends on 7)

The method of claim 7 wherein the adding step is accomplished by conducting the olefin metathesis reaction at a temperature between O and 150° C.

### Claim 11 (depends on 7)

The method of claim 7 wherein the adding step is accomplished by conducting the olefin metathesis reaction at a temperature between 40 and 120° C.

### Claim 12 (depends on 7)

The method of claim 7 wherein the adding step accomplished by conducting the olefin metathesis reaction between 1 minute and 24 hours.

### Claim 13 (depends on 1, 7)

The method of claim 7 wherein the adding step is accomplished by using the ruthenium complex according to claim 1 in a quantity of no more than 0.1 mol %.

### Claim 14 (depends on 1, 13)

The method of claim 13 wherein the using step is accomplish by adding the ruthenium complex according to claim 1 to the reaction mixture as a solid and/or as a solution in an organic solvent.

### Claim 15 (depends on 7)

The method of claim 7 wherein the adding step is accomplished by using a solution that is solvent-free.