Paracyclophane-based ligands, their preparation and use in catalysis

Patent metadata

Field	Value
Publication number	US-9340519-B2
Application number	US-201414336603-A
Country	US
Kind code	B2
Filing date	Jul 21, 2014
Priority date	Aug 29, 2007
Publication date	May 17, 2016
Grant date	May 17, 2016

Abstract

A substituted paracyclophane of formula (I) is provided

wherein X 1 and X 2 are linking groups comprising between 2 to 4 carbon atoms, Y 1 and Y 2 are selected from the group consisting of hydrogen, halide, oxygen, nitrogen, alkyl, cycloalkyl, aryl or heteroaryl and Z is a substituted or unsubstituted alkyl group, aryl group or heteroaryl group. The substituted paracyclophane provides transition metal catalysts that are useful in C—C and C—N bond formation and asymmetric hydrogenation reactions.

First claim

The invention claimed is:

1. A metal complex comprising the reaction product of a metal compound and a substituted paracyclophane of formula (I)

wherein X 1 and X 2 are linking groups comprising between 2 to 4 carbon atoms, Y 1 and Y 2 are selected from the group consisting of hydrogen, halide, oxygen, nitrogen, alkyl, cycloalkyl, aryl or heteroaryl, and Z is an unsubstituted alkyl group, a substituted aryl group, an unsubstituted aryl group, a substituted heteroaryl group, or an unsubstituted heteroaryl group,
wherein when Z is a substituted aryl group, the substituents are selected from the group consisting of halide, hydroxyl, alkoxy, carbonyl, carboxyl, anhydride, methacryl, epoxide, vinyl, nitrile, nitro, sulphate, sulphonyl, mercapto, amino, amine, imine, amide, and imide.

2. The metal complex according to claim 1 wherein the metal compound is a compound of palladium (Pd), platinum (Pt), rhodium (Rh), iridium (Ir) or ruthenium (Ru).

3. The metal complex according to claim 1 wherein the substituted paracyclophane (I) is substantially enantiomerically-pure.

4. The metal complex according to claim 1 wherein the metal complex is supported on a solid support.

5. The metal complex according to claim 2 wherein the substituted paracyclophane (I) is substantially enantiomerically-pure.

6. A method of asymmetrically hydrogenating a substrate, comprising performing the hydrogenation in the presence of a metal complex according to claim 2 .

7. A method of catalyzing a reaction, comprising performing the reaction in the presence of a metal complex according to claim 2 , wherein the reaction is selected from the group consisting of carbon-carbon coupling reactions, enantioselective isomerization of olefins, asymmetric hydroboration reactions, asymmetric cyclisation of olefinic aldehydes, asymmetric arylation reactions, asymmetric alkylation reactions and amination of aryl halides (Hartwig-Buchwald reaction).

8. The metal complex according to claim 1 , wherein X 1 and X 2 are both —C 2 H 4 —.

9. The metal complex according to claim 1 , wherein Z is a substituted or unsubstituted phenyl, naphthyl or anthracyl group.

10. The metal complex according to claim 1 , wherein Z is a substituted aryl group having one or more substituting groups selected from the group consisting of halide, hydroxyl, alkoxy, carbonyl, carboxyl, anhydride, methacryl, epoxide, vinyl, nitrile, nitro, sulphate, sulphonyl, mercapto, amino, amine, imine, amide and imide.

11. The metal complex according to claim 1 , wherein Z is a 2,5-disubstituted phenyl group.

12. The metal complex according to claim 8 , wherein Z is a substituted phenyl, naphthyl or anthracyl group.

13. The metal complex according to claim 8 , wherein Z is a substituted aryl group having one or more substituting groups selected from halide, hydroxyl, alkoxy, carbonyl, carboxyl, anhydride, methacryl, epoxide, vinyl, nitrile, nitro, sulphate, sulphonyl, mercapto, amino, amine, imine, amide and imide.

14. The metal complex according to claim 1 , wherein the substituted paracyclophane comprises:

Assignees

• Johnson Matthey Plc
• Johnson Matthey Plc

Inventors

• Xiao Jianliang
• Ruan Jiwu

Classifications

• B01J2531/0263

  Planar chiral ligands, e.g. derived from donor-substituted paracyclophanes and metallocenes or from substituted arenes · CPC title

• C07C41/30

  by increasing the number of carbon atoms, e.g. by oligomerisation · CPC title

• C07D295/033 Primary

  with the ring nitrogen atoms directly attached to carbocyclic rings · CPC title

• B01J2531/828

  Platinum · CPC title

• B01J2531/827

  Iridium · CPC title