# US 7,612,218 B2 · Process for production of heteroaryl-type boron compounds with iridium catalyst

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- Number: US 7,612,218 B2
- Document ID: US7612218B2
- Status: Granted
- Kind: B2
- Application number: 10/505,460
- Filed: 2003-03-05
- Published: 2005-07-07
- Granted: 2009-11-03
- Earliest claimed: 2002-03-06
- Assignees: Mitsubishi Rayon Co., Ltd.
- Inventors: Norio Miyaura; Tatsuo Ishiyama
- Web page: https://patentgrep.com/patent/US7612218B2

## CPC

- C07F 5/025: {Boronic and borinic acid compounds}
- B01J 31/1815: {with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine}
- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- B01J 23/468: {Iridium}
- B01J 2231/46: C-H or C-C activation
- B01J 2531/827: Iridium
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

The present invention provides an economically and industrially superior simple process that enables the selective production of an aromatic heterocyclic monoboron compound and aromatic heterocyclic diboron compound at a satisfactory yield and in a desired ratio by reacting an aromatic heterocyclic compound and a boron compound in a single step under mild conditions while changing only the charged ratios of the raw materials. The present invention provides a production process of a heteroaryl mono- or diboron compound comprising an aromatic heterocyclic compound and a boron compound in the form of bis(pinacolate)diboron or pinacolate diborane in the presence of a iridium-containing catalyst and a ligand such as a bipyridyl ligand.

## Claims

### Claim 1

A process of producing a heteroaryl boron compound represented by formula (V) or (VI):
wherein, X, Y, Z, R1 and R2 are the same as defined below, comprising:
reacting an aromatic heterocyclic compound represented with the following formula (I):
wherein X represents an oxygen atom or a sulfur atom, each of Y and Z represents —CH═, R1 and R2 may be the same or different and each represents a hydrogen atom, a linear or branched C1-8 alkyl group, a linear or branched C1-8 alkoxy group, a nitro group, a cyano group, a halogenated C1-8 alkyl group, a halogen atom, a carbamoyl group, a C1-8 acyl group, a C1-8 alkoxycarbonyl group, an amino group which may have a substituent,
with a boron compound represented with the following formula (III) or (IV):
in the presence of a univalent iridium complex catalyst of formula (X):
IrABn (X)
wherein A represents a chlorine atom, a linear or branched C1-8 alkoxy group, a hydroxyl group or a phenyloxy group which optionally has a substituent, B represents 1,5-cyclooctadiene or 1-cyclooctene, and n represents 1 or 2, or a univalent iridium complex catalyst in which the complexing ligand has formula:
wherein R3 represents a hydrogen atom, a linear or branched C1-8 alkyl group, a linear or branched C1-8 alkoxy group, a nitro group, a cyano group, a halogenated C1-8 alkyl group, a halogen atom, a carbamoyl group, a C1-8 acyl group, a C1-8 alkoxycarbonyl group, or an amino group which may or may not have a substituent.

### Claim 2 (depends on 1)

The process according to claim 1, wherein A of the iridium-containing catalyst is a methoxy group, B is 1,5-cyclooctadiene and n is 1.

### Claim 3 (depends on 1)

The process according to claim 1, wherein A of the iridium-containing catalyst is a chlorine atom, B is 1,5-cyclooctadiene and n is 1.

### Claim 4 (depends on 1)

The process according to claim 1, wherein A of the iridium-containing catalyst is a chlorine atom, B is 1-cyclooctene and n is 2.

### Claim 5 (depends on 1)

The process according to claim 1, wherein the ligand is 2,2′-bipyridine.

### Claim 6 (depends on 1)

The process according to claim 1, wherein the ligand is 4,4′-di-tert-butyl-2,2′-bipyridine.

### Claim 7 (depends on 1)

The process according to claim 1, wherein the reaction is carried out in the presence of solvent.

### Claim 8 (depends on 7)

The process according to claim 7, wherein the solvent is a hydrocarbon.