# US 9,751,848 B2 · Chelate-controlled diastereoselective hydrogenation with heterogeneous catalyst

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- Number: US 9,751,848 B2
- Document ID: US9751848B2
- Status: Granted
- Kind: B2
- Application number: 15/302,936
- Filed: 2015-09-28
- Published: 2017-02-02
- Granted: 2017-09-05
- Earliest claimed: 2014-09-26
- Assignees: Thomas Swan & Co. Ltd.
- Applicants: Thomas Swan & Co. Ltd
- Inventors: David Dunn; Howard Winston Tyrrell Sutton; John Ing Chuan Daly; Simon Jonathon Grant; Lian Hutchings; Patrice Georges Antonin Ribiere; Matthew Richard Gibbings; Sergio Aaron Gamboa Martinez; Craig Anderson; Yulia Rogan
- Web page: https://patentgrep.com/patent/US9751848B2

## CPC

- C07D 307/12: Radicals substituted by oxygen atoms
- B01J 23/58: with alkali- or alkaline earth metals
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

A catalyst, method of using, and use of a hydrogenation catalyst, preferably palladium on a support, preferably alumina or activated charcoal support. This in the presence of lithium salts, with salts such as the borates being preferred. This provides hydrogenation of precursors to give rise to a stereoselective, such as diastereoselective bias in the product of alkene hydrogenation using the catalyst. This equation, using the preferred substrate, best illustrates the invention:

## Claims

### Claim 1

A method of stereoselective hydrogenation, the method comprising providing a substrate of formula:
wherein Cycl represents an unsaturated moiety being a five or six membered heterocyclic ring and the heteroatom is selected from the group consisting of O, S, N and P; and R1 is selected from a group consisting of H, CH3, C1 to C6 alkyl chain, and C1 to C6 alkyl chain substituted with heteroatom selected from O, S, N, and P;
reacting the substrate with hydrogen under pressure in the presence of a catalyst composition, wherein no solvent is used, the catalyst composition comprising:
a metal hydrogenation catalyst on a support in the presence of a lithium salt.

### Claim 2 (depends on 1)

The method of claim 1 wherein the substrate is 2,2-di(2-furyl)propane to provide 2,2′-di(2-tetrahydrofuryl)propane.

### Claim 3 (depends on 2)

The method of claim 2 wherein the 2,2′-di(2-tetrahydrofuryl)propane product is present at more than 52% meso isomer.

### Claim 4 (depends on 1)

The method of claim 1 wherein the metal hydrogenation catalyst is selected from the group consisting of platinum, palladium, ruthenium, rhodium and nickel.

### Claim 5 (depends on 1)

The method of claim 1 wherein the catalyst is palladium.

### Claim 6 (depends on 1)

The method of claim 1 wherein the support is selected from the group consisting of carbon, alumina, silica, titanium dioxide, calcium carbonate, lithium aluminate and barium sulphate.

### Claim 7 (depends on 1)

The method of claim 1 wherein the support is selected from the group consisting of carbon and alumina.

### Claim 8 (depends on 1)

The method of claim 1 wherein the lithium salt is selected from the group consisting of an organo-carboxylate, an organo-sulphate, aluminate, chloride, bromide, carbonate, hydroxide, borate and a mixture thereof.

### Claim 9 (depends on 8)

The method of claim 8 wherein the lithium salt is selected from the group consisting of lithium tetraborate, metaborate, and their hydrates.

### Claim 10 (depends on 1)

The method of stereoselective hydrogenation of claim 1 wherein the substrate is 2, 2-di(2-furyl)propane, the catalyst is palladium,
the support is selected from the group consisting of carbon, alumina, silica, titanium dioxide, calcium carbonate, lithium aluminate and barium sulphate and
the lithium salt is selected from the group consisting of an organo-carboxylate, an organo-sulphate, aluminate, hydroxide, chloride, bromide, carbonate, hydroxide, borate and a mixture thereof.