Catalysts, ligands and use thereof

Patent metadata

Field	Value
Publication number	US-9636670-B2
Application number	US-201414784997-A
Country	US
Kind code	B2
Filing date	Apr 10, 2014
Priority date	Apr 18, 2013
Publication date	May 2, 2017
Grant date	May 2, 2017

Abstract

According to the present invention, there is provided a catalytic complex comprising a metal, one or more ligands and one or more counterions, wherein said one or more ligands include a non-racemic chiral ligand and wherein said one or more counterions include a triflimide counterion. Also provided are methods of making said catalytic complex and processes for producing chiral compounds which involve the use of said catalytic complex. In addition, the present invention provides compounds of the formula (2) as defined herein. The compounds of formula (2) may be useful as ligands in catalytic complexes.

First claim

The invention claimed is:

1. A compound of the formula (2):

wherein:
the moiety —O—C n —O— is chiral and is an aliphatic or aromatic diolate, wherein said diolate is optionally substituted;
each R E is the same and is an achiral substituted or unsubstituted alkyl organic group; and
each R F is the same and is an achiral substituted or unsubstituted aryl organic group; or R F and R F , together with the carbon atom to which they are attached, form an achiral substituted or unsubstituted cycloalkyl organic group;
or a salt thereof.

2. The compound according to claim 1 , wherein the moiety —O—C n —O— is a moiety derived from a binaphthol compound.

3. The compound according to claim 1 , wherein each R E is phenyl or naphthyl, either of which is optionally substituted.

4. The compound according to claim 3 , wherein each R E is phenyl or phenyl substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of C 1-6 alkyl, halogen, trifluoromethyl and C 1-6 alkoxy.

5. The compound according to claim 4 , wherein each R E is phenyl.

6. The compound according to claim 1 , wherein each R F is optionally substituted C 1-6 alkyl.

7. The compound according to claim 6 , wherein each R F is methyl.

8. The compound according to claim 1 , wherein R F and R F , together with the carbon atom to which they are attached, form an optionally substituted cycloalkyl group.

9. The compound according to claim 1 , wherein each R E is optionally substituted phenyl or naphthyl; and each R F is optionally substituted C 1-6 alkyl, or R F and R F , together with the carbon atom to which they are attached, form an optionally substituted cycloalkyl group.

10. The compound according to claim 1 , wherein each R E is optionally substituted phenyl; and each R F is optionally substituted C 1-6 alkyl, or R F and R F , together with the carbon atom to which they are attached, form cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, any of which is optionally substituted.

11. The compound according to claim 1 , wherein each R E is phenyl or phenyl substituted with 1, 2, 3, 4 or 5 substituents independently selected from C 1-6 alkyl, halogen, trifluoromethyl and C 1-6 alkoxy; and each R F is methyl.

12. The compound according to claim 1 , wherein the compound is a compound of formula (C) or (D):

13. A catalytic complex comprising a metal and a ligand, wherein said ligand is a compound of claim 1 .

14. The catalytic complex according to claim 13 , wherein the catalytic complex further comprises a counterion.

15. The catalytic complex according to claim 14 , wherein the counterion is a triflimide counterion.

16. The catalytic complex according to claim 14 , wherein said catalytic complex is of the formula M′L′Z′, wherein M′ is a metal, L′ is a ligand which is said compound, and Z′ is a counterion.

17. The catalytic complex according to claim 13 , wherein the metal is a transition metal.

18. A process for producing a chiral compound in a stereoisomeric excess;
wherein the process comprises:
contacting a first compound comprising an alkene bond with a hydrometallating agent, wherein the first compound and the hydrometallating agent are contacted under conditions such that the first compound is hydrometallated by said hydrometallating agent; and
(ii) contacting the hydrometallated first compound with a second compound, wherein the second compound comprises a conjugated π-bond system which is capable of undergoing a 1,4-conjugate addition reaction or a 1,6-conjugate addition reaction and which has a carbon atom at said 4- or 6-position respectively, wherein the hydrometallated first compound and the second compound are contacted under conditions such that they undergo an asymmetric 1,4-conjugate addition reaction or an asymmetric 1,6-conjugate addition reaction in which a carbon atom of said hydrometallated first compound binds to the carbon atom at said 4-position or said 6-position of the second compound, forming a stereoisomeric excess of a compound having a chiral carbon atom at said 4-position or said 6-position;
wherein said asymmetric 1,4-conjugate addition reaction or said asymmetric 1,6-conjugate addition reaction is performed in the presence of the catalytic complex of claim 13 .

19. The process according to claim 18 , wherein a quaternary centre is formed at the carbon atom at said 4-position or said 6-position.

20. The compound according to claim 2 , wherein the moiety —O—C n —O— is a moiety derived from (R)-1,1′-bi-2-naphthol or (S)-1,1′-bi-2-naphthol.

21. The compound according to claim 6 , wherein each R F is optionally substituted methyl, ethyl or propyl.

Assignees

• Fletcher Stephen Patrick
• Maksymowicz Rebecca Marie
• Roth Philippe Marie-Christophe
• Portela Mireia Sidera
• Univ Oxford Innovation Ltd

Inventors

• Fletcher Stephen Patrick
• Maksymowicz Rebecca Marie
• Roth Philippe Marie-Christophe
• Portela Mireia Sidera

Classifications

• B01J31/0224 Primary

  being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds · CPC title

• B01J31/188

  Amide derivatives thereof · CPC title

• B01J2231/32

  Addition reactions to C=C or C-C triple bonds · CPC title

• C07C49/84

  containing ether groups, [IMAGE cpc-sch-C07C-0958.gif] groups,[IMAGE cpc-sch-C07C-0959.gif] groups, or[IMAGE cpc-sch-C07C-0960.gif] groups · CPC title

• B01J31/1855 Primary

  Triamide derivatives thereof · CPC title