Process for preparing diene

Patent metadata

Field	Value
Publication number	US-12103898-B2
Application number	US-202118007339-A
Country	US
Kind code	B2
Filing date	Jul 26, 2021
Priority date	Jul 30, 2020
Publication date	Oct 1, 2024
Grant date	Oct 1, 2024

Abstract

The present invention relates to the field of organic synthesis and more specifically it concerns a process for preparing compound of formula (I) catalyzed by a nickel complex. The compound of formula (II) is also part of the invention.

First claim

The invention claimed is:

1. A process for the preparation of a compound of formula (I)

in a form of any one of its stereoisomers or a mixture thereof and wherein the dotted line is a carbon-carbon double or a carbon-carbon triple bond and R 1 represents a C 1-10 hydrocarbon group, optionally comprising one or more hydroxy, C 1-15 alkoxy, C 2-15 alkenyloxy, C 3-15 heterocycloalkyl, C 6-10 aryloxy and/or C 1-4 carboxylic ester groups and R 2 , R 3 , R 4 and R 5 , independently from each other, represent a hydrogen atom, a C 1-3 alkyl group or a phenyl group;
comprising the reaction of a compound of formula (II)

in a form of any one of its stereoisomers and wherein the dotted line, R 1 , R 2 , R 3 , R 4 and R 5 have the same meaning as defined in formula (I) and X represents a OR 6 group, a OC(═O)R 6 group, a OC(═O)OR 6 group or a OSO 2 R 6 group, wherein R 6 is a hydrogen atom or a C 1-4 alkyl group or a phenyl group;
with a nickel catalyst.

2. The process according to claim 1 , wherein R 1 represents a linear C 1-10 alkyl group, a linear C 2-10 alkenyl group, a branched C 3-10 alkyl or alkenyl group, or a C 6-10 aryl group, optionally comprising one hydroxy or C 1-4 carboxylic ester group.

3. The process according to claim 1 , wherein R 1 represents a linear C 4-8 alkyl group.

4. The process according to according to claim 1 , wherein X represents a OC(═O)R 6 group wherein R 6 is a C 1-3 alkyl group.

5. The process according to claim 1 , wherein X represents an acetate group.

6. The process according to claim 1 , wherein each of R 2 , R 3 , R 4 and R 5 are a hydrogen atom.

7. The process according to claim 1 , wherein the nickel catalyst is of formula
[Ni(P) 4 ]  (III) or

[Ni(PP) 2 ]  (III′) . . . or

[Ni(P) 2 ML]  (III″) or

[Ni(PP)ML]  (III′″)

wherein each P represents, independently from each other, a C 3 -C 30 monodentate ligand wherein the coordinating groups are one phosphorus atom and each PP represents, independently from each other, a C 5 -C 50 bidentate ligand wherein the coordinating groups are two phosphorus atoms; and M and L, independently from each other, are an anionic or neutral ligand, provided that when M is a neutral ligand, L is a neutral ligand and when Mis an anionic ligand, L is an anionic ligand.

8. The process according to claim 7 , wherein P is a monophosphite of formula P(OR 7 ) 3 wherein R 7 is C 1-6 linear alkyl group, a C 3-6 branched alkyl group or a phenyl group.

9. The process according to claim 7 , wherein the nickel catalyst of formula (III), (III′) (III″) or (III′″) is formed in situ by the reaction between a nickel(II) complex and a phosphite or phosphine in the presence of a base.

10. The process according to claim 1 , wherein the compound of formula (I) is of formula

in a form of any one of its stereoisomers or a mixture thereof and wherein R 1 represents a C 1-10 hydrocarbon group, optionally comprising one or more hydroxy, C 1-15 alkoxy, C 2-15 alkenyloxy, C 3-15 heterocycloalkyl, C 6-10 aryloxy and/or C 1-4 carboxylic ester groups and R 2 , R 3 , R 4 and R 5 , independently from each other, represent a hydrogen atom, a C 1-3 alkyl group or a phenyl group; and
the compound of formula (II) is of formula

in a form of any one of its stereoisomers and wherein R 1 , R 2 , R 3 , R 4 , R 5 and X have the same meaning as defined in formula (I′).

11. The process according to claim 1 , wherein the compound of formula (I) is of formula

in a form of any one of its stereoisomers or a mixture thereof and wherein R 1 represents a C 1-10 hydrocarbon group, optionally comprising one or more hydroxy, C 1-15 alkoxy, C 2-15 alkenyloxy, C 3-15 heterocycloalkyl, C 6-10 aryloxy and/or C 1-4 carboxylic ester groups and R 2 , R 3 , R 4 and R 5 , independently from each other, represent a hydrogen atom, a C 1-3 alkyl group or a phenyl group; and
the compound of formula (II) is of formula

in a form of any one of its stereoisomers and wherein R 1 , R 2 , R 3 , R 4 , R 5 and X have the same meaning as defined in formula (I′).

12. The process according to claim 11 , wherein the compound of formula (II″) is obtained by the reduction of the compound of formula (II′).

13. A process for the preparation of a compound of formula (IV)

in a form of any one of its stereoisomers and wherein R 1 represents a C 1-10 hydrocarbon group, optionally substituted by one or more hydroxy, C 1-15 alkoxy, C 2-15 alkenyloxy, C 3-15 heterocycloalkyl, C 6-10 aryloxy and/or C 1-4 carboxylic ester groups; R 2 , R 3 and R 4 , independently from each other, represent a hydrogen atom, a C 1-3 alkyl group or a phenyl group and Y is a hydrogen atom, a C 1-3 alkyl group, or a CHR 5 X group wherein R 5 is a hydrogen atom, a C 1-3 alkyl group or a phenyl group and X represents a OR 6 group, a OC(═O)R 6 group, a OC(═O)OR 6 group or a OSO 2 R 6 group, wherein R 6 is a hydrogen atom or a C 1-4 alkyl group or a phenyl group;
by reacting together a compound of formula

in a form of any one of its stereoisomers and wherein R 1 has the same meaning as defined in formula (IV);
with a compound of formula

in a form of any one of its stereoisomers and wherein X, Y, R 2 , R 3 and R 4 have the same meaning as defined in formula (IV);
in the presence of a nickel catalyst.

14. The process according to claim 13 , wherein the nickel catalyst is of formula
[Ni(P) 4 ]  (III) or

[Ni(PP) 2 ]  (III′) . . . or

[Ni(P) 2 ML]  (III″) or

[Ni(PP)ML]  (III′″)

wherein each P represents, independently from each other, a C 3 -C 30 monodentate ligand wherein the coordinating groups are one phosphorus atom and each PP represents, independently from each other, a C 5 -C 50 bidentate ligand wherein the coordinating groups are two phosphorus atoms; and M and L, independently from each other, are an anionic or neutral ligand, provided that when M is a neutral ligand, L is a neutral ligand and when Mis an anionic ligand, L is an anionic ligand.

15. A compound of formula

in a form of any one of its stereoisomers and wherein the dotted line is a carbon-carbon double or a carbon-carbon triple bond; R 1 represents a linear or branched C 1-10 alkyl group, optionally substituted by one or more hydroxy, C 1-15 alkoxy, C 2-15 alkenyloxy, C 3-15 heterocycloalkyl, C 6-10 aryloxy and/or C 1-4 carboxylic ester groups; R 2 , R 3 , R 4 and R 5 , independently from each other, represent a hydrogen atom, a C 1-3 alkyl group or a phenyl group and X represents a OR 6 group, a OC

Assignees

• Firmenich & Cie

Inventors

• Jacoby Denis
• Dupau Philippe
• Bonomo Lucia
• Chappuis Simone
• Blanchard Virginie

Classifications

• C07C2523/44

  Palladium · CPC title

• C07C67/293

  by isomerisation; by change of size of the carbon skeleton · CPC title

• C07C11/21

  Alkatrienes; Alkatetraenes; Other alkapolyenes · CPC title

• C07C2527/128

  Compounds comprising a halogen and an iron group metal or a platinum group metal · CPC title

• C07C1/213 Primary

  by splitting of esters · CPC title