Process for preparing bicyclic enolether

Patent metadata

Field	Value
Publication number	US-10858370-B2
Application number	US-201816637484-A
Country	US
Kind code	B2
Filing date	Oct 8, 2018
Priority date	Nov 1, 2017
Publication date	Dec 8, 2020
Grant date	Dec 8, 2020

Abstract

Described herein is a process for preparing a compound of formula (I) starting from a compound of formula (II), where the process is catalyzed by a Ruthenium complex.

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 R 1 represents a linear or branched C 1-5 alkanediyl or alkenediyl group, optionally substituted by a phenyl group and R 2 represents a linear or branched C 1-10 alkanediyl or alkenediyl group, optionally substituted by a phenyl group, the process comprising
reacting a compound of formula (II)

in a form of any one of its stereoisomers and wherein R 1 and R 2 have the same meaning as defined in formula (I)
with a ruthenium catalyst and in the presence of a base and a hydrogen source.

2. The process according to claim 1 , characterized in that R 1 represents a linear or branched C 1-4 alkanediyl group.

3. The process according to claim 1 , characterized in that R 1 represents a linear or branched C 2-3 alkanediyl group.

4. The process according to according to claim 1 , characterized in that R 1 represents a 1,2-propanediyl group or 1,2-ethanediyl group.

5. The process according to claim 1 characterized in that R 2 represents a linear or branched C 4-9 alkanediyl group.

6. The process according to claim 1 , characterized in that R 2 represents a linear or branched C 6-9 alkanediyl group.

7. The process according to claim 1 , characterized in that R 2 represents a 1,8-octanediyl group.

8. The process according to claim 1 , characterized in that compound of formula (I) is selected from the group consisting of 12-oxabicyclo[6.3.1]dodec-8-ene, 10-methyl-12-oxabicyclo[6.3.1]dodec-8-ene, 13-oxabicyclo[7.3.1]tridec-9-ene, 11-methyl-13-oxabicyclo[7.3.1]tridec-9-ene, 14-oxabicyclo[8.3.1]tetradec-10-ene, 12-methyl-14-oxabicyclo[8.3.1]tetradec-10-ene, 15-oxabicyclo[9.3.1]pentadec-11-ene, 13-methyl-15-oxabicyclo[9.3.1]pentadec-11-ene, 16-oxabicyclo[10.3.1]hexadec-12-ene, 14-methyl-16-oxabicyclo[10.3.1]hexadec-12-ene, 17-oxabicyclo[11.3.1]heptadec-13-ene, and 15-methyl-17-oxabicyclo[11.3.1]heptadec-13-ene.

9. The process according to claim 1 , characterized in that compound of formula (II) is selected from the group consisting of cycloundecane-1,5-dione, 3-methylcycloundecane-1,5-dione, cyclododecane-1,5-dione, 3-methycyclododecane-1,5-dione, cyclotridecane-1,5-dione, 3-methycyclotridecane-1,5-dione, cyclotetradecane-1,5-dione, 3-methycyclotetradecane-1,5-dione, cyclopentadecane-1,5-dione, 3-methycyclopentadecane-1,5-dione, cyclohexadecane-1,5-dione, and 3-methycyclohexadecane-1,5-dione.

10. The process according to claim 1 , characterized in that the ruthenium catalyst is of formula
[Ru(X) 2 P n ]  (III)

wherein X represents an anionic ligand; and
when n is an integer between 1 to 4, P represents a monophosphine monodendate ligand or when n is an integer between 1 to 2, P represents a biphosphine bidentate ligand.

11. The process according to claim 1 , characterized in that the ruthenium catalyst is selected from the group consisting of [Ru(H)(Cl)(PPh 3 ) 3 ], [Ru(H) 2 (PPh 3 ) 3 ], [Ru(OAc) 2 (PPh 3 ) 2 ], [Ru(OPiv) 2 (PPh 3 ) 2 ], [Ru(Cl) 2 (PBu 3 ) 3 ], and [Ru(Cl) 2 (PPh 3 ) 3 ].

12. The process according to claim 1 , characterized in that the base is selected from the group consisting of pyridine, trimethylamine, lutidine, N,N-Diisopropylethylamine, 1,8-Diazabicyclo[5.4.0]undec-7-ene, alkali metal alkoxide, carboxylate, carbonate, or hydroxide, and a mixture thereof.

13. The process according to claim 1 , characterized in that the hydrogen source is a hydrocarbon comprising at least one secondary alcohol functional group and having a boiling point equal to or above 110° C.

14. The process according to claim 1 , characterized in that the hydrogen source is of formula

wherein R 3 and R 4 , independently from each other, represent a C 1-10 linear alkyl group optionally substituted by a hydroxy group or an aryl group, a C 2-10 linear alkenyl group optionally substituted by a hydroxy group or an aryl group, a C 3-10 branched or cyclic alkyl or alkenyl group optionally substituted by a hydroxy group or an aryl group, or a phenyl group optionally substituted by one to five C 1-3 alkyl or alkoxy groups, hydroxy groups or halogen atoms; or R 3 and R 4 , when taken together, represent a C 2-10 linear or branched alkanediyl or alkenediyl optionally substituted by a hydroxy group or an aryl group.

15. The process according to claim 1 , characterized in that the hydrogen source is 1-phenylethan-1-ol, 2-methyl-2,4-pentanediol, cyclohexanol, 4-methylpentan-2-ol, cyclopentanol, or octan-2-ol.

Assignees

• Firmenich & Cie

Inventors

• Jacoby Denis
• Fankhauser Peter

Classifications

• C07D493/08 Primary

  Bridged systems · CPC title

• B01J31/24

  Phosphines {, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands} · CPC title