# US 9,433,937 B2 · Water-insoluble ruthenium catalyst composition for use in aqueous hydrogenation reactions

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- Number: US 9,433,937 B2
- Document ID: US9433937B2
- Status: Granted
- Kind: B2
- Application number: 14/772,393
- Filed: 2014-03-05
- Published: 2016-01-14
- Granted: 2016-09-06
- Earliest claimed: 2013-03-06
- Assignees: Dexlechem GMBH
- Applicants: Dexlechem GMBH
- Inventors: Sonja Jost
- Web page: https://patentgrep.com/patent/US9433937B2

## CPC

- C07C 29/143: of ketones
- B01J 31/2409: {with more than one complexing phosphine-P atom}
- B01J 31/2457: {comprising aliphatic or saturated rings, e.g. Xantphos}
- C07C 29/145: with hydrogen or hydrogen-containing gases
- C07C 67/31: by introduction of functional groups containing oxygen only in singly bound form
- C07F 15/0046: {Ruthenium compounds}
- B01J 2231/643: of R2C=O or R2C=NR (R= C, H)
- B01J 2531/0266: Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
- B01J 2531/821: Ruthenium
- B01J 2531/90: Catalytic systems characterized by the solvent or solvent system used
- B01J 2531/96: Water
- C07B 2200/07: Optical isomers
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)

## Abstract

The invention relates to a method for converting a precatalyst complex to an active catalyst complex, wherein the precatalyst complex and the active catalyst complex comprise a ruthenium atom and an optically active ligand that is insoluble in water, and the active catalyst complex furthermore comprises a monohydride and a water molecule. The method comprises the steps of providing water as an activation solvent system with a pH value equal or below 2, and solving said precatalyst complex, an acid, and hydrogen therein. The invention further relates to a method for manufacturing a catalyst composition, a method for hydrogenating a substrate molecule and a reaction mixture.

## Claims

### Claim 1

A method for converting a precatalyst complex to an active catalyst complex,
wherein said precatalyst complex and said active catalyst complex comprise a ruthenium atom and an optically active ligand that is insoluble in water, and
wherein said active catalyst complex comprises a monohydride and a water molecule, said method comprising the steps of:
a) providing an activation solvent system comprising water,
b) adding to, particularly solving in, said activation solvent system
said precatalyst complex,
a solubilizer,
an acid, and
hydrogen,
characterized in that
the pH value of said activation solvent system is equal or below 2 after addition of said acid.

### Claim 2 (depends on 1)

The method according to claim 1, wherein said activation solvent system comprises ≧50% (v/v), ≧75% (v/v), ≧80% (v/v), ≧90% (v/v), ≧99% (v/v) or 100% water.

### Claim 3 (depends on 1)

The method according to claim 1, wherein said solubilizer is a surfactant that is capable of forming micelles in water and that is resistant to hydrolysis at pH≦2.

### Claim 4 (depends on 1)

The method according to claim 1, wherein said optically active ligand is selected from the group consisting of:
5,5′-bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxane;
(5,5′-bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole;
2,2′-bis(diphenylphosphino)-1,1′-binaphthyl;
O-isopropyliden-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane;
ethane-1,2-diylbis[(2-methoxyphenyl)phenylphosphane];
(bis(diphenylphosphino)butane;
(3-diphenylphosphanyl-2-bicyclo[2.2.1]hept-5-enyl)-diphenyl-phosphane;
(1-benzyl-4-diphenylphosphanyl-pyrrolidin-3-yl)-diphenyl-phosphane;
(2-diphenylphosphanyl-1-methyl-ethyl)-diphenyl-phosphane;
[2-(diphenylphosphanylmethyl)cyclohexyl]methyl-diphenyl-phosphane;
tert-butyl 4-benzhydryl-2-(2,2-diphenylethyl)pyrrolidine-1-carboxylate;
[2-(1-naphthyl)phenyl]-[2-[2-(1-naphthyl)phenyl]phosphanylethyl]phosphane,
[2-(2-diphenylphosphanyl-6-methoxy-phenyl)-3-methoxy-phenyl]-diphenyl-phosphane;
[4-chloro-2-(3-chloro-6-diphenylphosphanyl-2-methoxy-phenyl)-3-methoxy-phenyl]-diphenyl-phosphane;
[5-chloro-2-(4-chloro-2-diphenylphosphanyl-6-methoxy-phenyl)-3-methoxy-phenyl]-diphenyl-phosphane;
[2-(6-diphenylphosphanyl-2,3,4-trimethyl-phenyl)-3,4,5-trimethyl-phenyl]-diphenyl-phosphane;
[3-(4-diphenylphosphanyl-2,6-dimethoxy-3-pyridyl)-2,6-dimethoxy-4-pyridyl]-diphenyl-phosphane;
[4-(4-diphenylphosphanyl-2,5-dimethyl-3-thienyl)-2,5-dimethyl-3-thienyl]-diphenyl-phosphane;
[8-(7-diphenylphosphanyl-4-methyl-2,3-dihydro-1,4-benzoxazin-8-yl)-4-methyl-2,3-dihydro-1,4-benzoxazin-7-yl]-diphenyl-phosphane; and
a compound characterized by formula III:
wherein n is 1, 2, 3, 4, 5 or 6.