# US 11,077,433 B2 · Production of fatty olefin derivatives via olefin metathesis

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- Number: US 11,077,433 B2
- Document ID: US11077433B2
- Status: Granted
- Kind: B2
- Application number: 16/798,954
- Filed: 2020-02-24
- Published: 2020-08-20
- Granted: 2021-08-03
- Earliest claimed: 2015-11-18
- Assignees: Provivi, Inc.
- Applicants: Provivi, Inc.
- Inventors: Keith M. Wampler; Peter Meinhold; Pedro Coelho; Vu Bui; Levente Ondi; Hasan Mehdi
- Web page: https://patentgrep.com/patent/US11077433B2

## 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 1

A method for synthesizing a compound according to Formula VIb:
the method comprising:
acylating an alkenol according to Formula VIII
to form an acylated alkenol according to Formula IX
and
contacting the acylated alkenol with an olefin according to Formula I
in the presence of a metathesis catalyst having a structure according to Formula 2a
thereby forming the compound of Formula VIb; wherein:
R1 is selected from the group consisting of H, C1-18 alkyl, and C2-18 alkenyl;
R2c is C1-6 acyl,
subscript y is an integer ranging from 0 to 17;
subscript z is an integer ranging from 0 to 17;
M is Mo or W;
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 2 (depends on 1)

The method of claim 1, wherein the alkenol according to Formula VIII is formed by reducing an alkyl ester according to Formula IIb:
wherein R2b is C1-8 alkyl.

### Claim 3 (depends on 1)

The method of claim 1, wherein the compound of Formula VIb is selected from (Z)-7-dodecenyl acetate; (E)-7-dodecenal; (Z)-7-decenyl acetate; (Z)-7-hexadecenal; (Z)-7-hexadecenyl acetate; (Z)-7-tetradecenal; (Z)-7-tetradecenyl acetate; (Z)-7-undecenyl acetate; (Z)-10-dodecenyl acetate; (Z)-10-hexadecenyl acetate; (Z)-10-pentadecenal; (Z)-10-pentadecenyl acetate; (Z)-10-tetradecenyl acetate; (Z)-10-tridecenyl acetate; (Z)-9-dodecenal; (Z)-9-dodecenyl acetate; (Z)-9-hexadecenal; (Z)-9-hexadecenyl acetate; (Z)-9-pentadecenyl acetate; (Z)-9-tetradecenal; (Z)-9-tetradecenyl acetate; (Z)-9-tetradecenyl formate; (Z)-9-tetradecenyl nitrate; (Z)-9-tridecenyl acetate; (Z)-9-undecenyl acetate; (Z)-11-hexadecen-1-ol; (Z)-11-hexadecenal; (Z)-11-hexadecenyl acetate; (Z)-11-tetraceden-1-ol; (Z)-11-tetracedenyl acetate; (Z)-13-octadecen-1-ol; and (Z)-13-octadecenal.

### Claim 4 (depends on 1)

The method of claim 1, wherein:
R7a is pyrrolyl, imidazolyl, pyrazolyl, azaindolyl, or indazolyl, each of which is optionally substituted; and
R5a is a hydrogen atom.

### Claim 5 (depends on 1)

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

### Claim 6 (depends on 5)

The method of claim 5, wherein R8a is:

### Claim 7 (depends on 1)

The method of claim 1, wherein R4b is methoxy, R4c is hydrogen, and R4d is hydrogen.

### Claim 8 (depends on 1)

The method of claim 1, wherein the metathesis catalyst is:

### Claim 9 (depends on 1)

The method of claim 1, wherein the catalyst is present in an amount less than 0.01 mol % with respect to the olefin or to the metathesis reaction partner.

### Claim 10 (depends on 3)

The method of claim 3, wherein the compound of Formula VIb comprises at least 80% Z olefin.

### Claim 11 (depends on 1)

The method claim 1, wherein acylating the alkenol according to Formula VIII is conducted with an acylating agent selected from the group consisting of acetic anhydride and acetyl chloride.

### Claim 12 (depends on 11)

The method claim 11, wherein 1-5 molar equivalents of the acylating agent with respect to the alkenol according to Formula VIII is used.