# US 2022/0032280 A1 · Production of fatty olefin derivatives via olefin metathesis

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- Number: US 2022/0032280 A1
- Document ID: US20220032280A1
- Status: Published application
- Kind: A1
- Application number: 17/390,136
- Filed: 2021-07-30
- Published: 2022-02-03
- Earliest claimed: 2015-11-18
- Assignees: Provivi, Inc.; XiMo AG
- Applicants: Provivi, Inc.
- Inventors: Keith M. Wampler; Peter Meinhold; Pedro Coelho; Vu Bui; Hasan Mehdi
- Web page: https://patentgrep.com/patent/US20220032280A1

## CPC

- B01J 31/2278: {Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts}
- C07C 6/04: at a carbon-to-carbon double bond
- C07C 29/147: of carboxylic acids or derivatives thereof
- C07C 45/41: by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
- C07C 67/08: by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
- C07C 67/293: by isomerisation; by change of size of the carbon skeleton
- C07C 67/343: by increase in the number of carbon atoms
- B01J 2231/543: alkene metathesis
- B01J 2531/64: Molybdenum
- B01J 2531/66: Tungsten
- C07B 2200/09: Geometrical isomers
- C07C 2531/22: Organic complexes
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)

## Abstract

In one aspect, the invention provides a method for synthesizing a fatty olefin derivative. The method includes: a) contacting an olefin according to Formula I with a metathesis reaction partner according to Formula IIb in the presence of a metathesis catalyst under conditions sufficient to form a metathesis product according to Formula IIIb: and b) converting the metathesis product to the fatty olefin derivative. Each R1 is independently selected from H, C1-18 alkyl, and C2-18 alkenyl; R2b is C1-8 alkyl; subscript y is an integer ranging from 0 to 17; and subscript z is an integer ranging from 0 to 17. In certain embodiments, the metathesis catalyst is a tungsten catalyst or a molybdenum catalyst. In various embodiments, the fatty olefin derivative is a pheromone. Pheromone compositions and methods of using them are also described.

## Claims

### Claim at position 1

1-10. (canceled)

### Claim 11

A method for synthesizing a fatty olefin derivative, the method comprising:
a) contacting an olefin according to Formula I
wherein
R1 is C1-18 alkyl, and
subscript z is an integer ranging from 0 to 17,
with a metathesis reaction partner according to Formula IIb
wherein
R1 is selected from the group consisting of H, C1-18 alkyl, and C2-18 alkenyl,
R2b is C1-8 alkyl, and
subscript y is an integer ranging from 0 to 17,
in the presence of a metathesis catalyst to form a metathesis product according to Formula IIIb:
and
b) converting the metathesis product to the fatty olefin derivative;
wherein the fatty olefin derivative is selected from the group consisting of an unsaturated fatty alcohol, an unsaturated fatty alcohol acetate, an unsaturated fatty aldehyde, and an unsaturated fatty acid ester; and
wherein the metathesis catalyst is selected from the group consisting of a Z-selective tungsten metathesis catalyst, a Z-selective molybdenum metathesis catalyst, or a Z-selective ruthenium metathesis catalyst.

### Claim 12 (depends on 11)

The method of claim 11, wherein converting the metathesis product to the fatty olefin derivative comprises reducing the metathesis product to form an unsaturated fatty alcohol according to Formula Vc:

### Claim 13 (depends on 12)

The method of claim 12, wherein the unsaturated fatty alcohol is the fatty olefin derivative.

### Claim 14 (depends on 13)

The method of claim 13, wherein R2b is methyl, subscript y is 7, and subscript z is 3.

### Claim 15 (depends on 12)

The method of claim 12, wherein converting the metathesis product to the fatty olefin derivative further comprises acylating the unsaturated fatty alcohol, thereby forming an unsaturated fatty alcohol acetate according to Formula VIb:
wherein R2c is C1-6 acyl, and
wherein the unsaturated fatty alcohol acetate is the fatty olefin derivative.

### Claim 16 (depends on 15)

The method of claim 15, wherein R2b is methyl, subscript y is 7, subscript z is 3, and R2c is acetyl.

### Claim 17 (depends on 12)

The method of claim 12, wherein converting the metathesis product to the fatty olefin derivative further comprises oxidizing the unsaturated fatty alcohol, thereby forming an unsaturated fatty aldehyde according to Formula VIIc:
wherein the unsaturated fatty aldehyde is the fatty olefin derivative.

### Claim 18 (depends on 11)

The method of claim 11, wherein converting the metathesis product to the fatty olefin derivative further comprises reducing the metathesis product, thereby forming a fatty olefin derivative according to Formula VIII:

### Claim 19 (depends on 18)

The method of claim 18, wherein R1 is H, R2b is methyl, subscript y is 7, and subscript z is 3.

### Claim 20 (depends on 11)

The method of claim 11, wherein the metathesis catalyst has a structure according to Formula 2:
wherein:
M is Mo or W;
R3a is selected from the group consisting of aryl, heteroaryl, alkyl, heteroalkyl, cycloalkyl, and heterocycloalkyl, each of which is optionally substituted;
R4a and R5a are independently selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted aryl, and optionally substituted heteroaryl;
R7a is selected from the group consisting of alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, and silyloxy, each of which is optionally substituted; and
R6a is R8A—X—, wherein
X is O or S and R8a is optionally substituted aryl; or
X is O and R8a is SiR9aR10aR11a or CR12aR13aR14a, wherein R9a, R10a, R11a, R12a, R13a and R14a are independently selected from the group consisting of optionally substituted alkyl and optionally substituted phenyl; or
R6a and R7a are linked together and are bonded to M via oxygen.

### Claim 21 (depends on 20)

The method of claim 20, wherein:
R7a is selected from the group consisting of alkyl, alkoxy, heteroalkyl, aryl, aryloxy, and heteroaryl, each of which is optionally substituted; and
X is O or S and R8a is optionally substituted aryl; or
X is O and R8a is CR12aR13aR14a.

### Claim 22 (depends on 20)

The method of claim 20, wherein
R3a is selected from the group consisting of 2,6-dimethylphenyl; 2,6-diisopropylphenyl;
2,6-dichlorophenyl; and adamant-1-yl;
R4a is selected from the group consisting of —C(CH3)2C6H5 and —C(CH3)3;
R5a is H;
R7a is selected from the group consisting of pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluorene-9-yloxy; 2,6-diphenyl-phenoxy; and t-butyloxy; and
R8a is R8a—X—, wherein
X═O and
R8a is phenyl which bears two substituents in the ortho positions with respect to O, or which bears at least three substituents, from which two substituents are in the ortho positions with respect to O and one substituent is in the para position with respect to O; or
R8a is selected from the group consisting of optionally substituted 8-(naphthalene-1-yl)-naphthalene-1-yl; optionally substituted 8-phenlynaphthalene-1-yl; optionally substituted quinoline-8-yl; triphenylsilyl; triisopropylsilyl; triphenylmethyl; tri(4-methylphenyl)methyl; 9-phenyl-fluorene-9-yl; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yl; and t-butyl.

### Claim 23 (depends on 22)

The method of claim 22, wherein:
R7a is selected from the group consisting of pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; and
R8a is phenyl which bears two substituents in the ortho positions with respect to O, or which bears at least three substituents, from which two substituents are in the ortho positions with respect to O and one substituent is in the para position with respect to O; or
R8a is selected from the group consisting of optionally substituted 8-(naphthalene-1-yl)-naphthalene-1-yl and optionally substituted 8-phenlynaphthalene-1-yl.

### Claim 24 (depends on 20)

The method of claim 20, wherein the metathesis catalyst has a structure according to Formula 2a:
wherein:
R3a is aryl, heteroaryl, alkyl, or cycloalkyl, each of which is optionally substituted;
R7a is pyrrolyl, imidazolyl, indolyl, pyrazolyl, azaindolyl, or indazolyl, each of which is optionally substituted;
R8a is optionally substituted aryl;
R5a is a hydrogen atom, alkyl, or alkoxy;
R4b is a hydrogen atom, —O—(C1-6 alkyl), —CH2—O—(C1-6 alkyl), heteroalkoxy, or —N(C1-6 alkyl)2; and
R4c and R4d are independently a hydrogen atom, C1-6 alkyl, C1-6 alkoxy, a halogen atom, —NO2, an amide, or a sulfonamide.

### Claim 25 (depends on 24)

The method of claim 24, wherein:
R7a is pyrrolyl, imidazolyl, pyrazolyl, azaindolyl, or indazolyl, each of which is optionally substituted; and
R5a is a hydrogen atom.

### Claim 26 (depends on 24)

The method of claim 24, wherein R3a is phenyl, 2,6-dichlorophenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2-trifluoromethylphenyl, pentafluorophenyl, tert-butyl, or 1-adamantyl.

### Claim 27 (depends on 26)

The method of claim 26, wherein R8a is

### Claim 28 (depends on 27)

The method of claim 27, wherein R4b is methoxy, R4c is hydrogen, and R4d is hydrogen.

### Claim 29 (depends on 20)

The method of claim 20, wherein the metathesis catalyst is selected from the group consisting of

### Claim 30 (depends on 11)

The method of claim 11, wherein the catalyst is present in an amount less than 0.01 mol % with respect to the olefin or to the metathesis reaction partner.