Method of preparing silylative-reduced N-heterocyclic compound using organoboron catalyst

Patent metadata

Field	Value
Publication number	US-9745329-B1
Application number	US-201514891096-A
Country	US
Kind code	B1
Filing date	Jan 29, 2015
Priority date	Nov 11, 2014
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

Abstract

Provided is a method of preparing a silylative-reduced N-heterocyclic compound by reducing an N-heteraromatic compound including a sp 2 hybridized nitrogen atom while simultaneously introducing a silyl group into a beta-position with respect to a nitrogen atom of the N-heteroaromatic compound, using a silane compound, in the presence of an organoboron catalyst.

First claim

The invention claimed is:

1. A method of preparing a silylative-reduced N-heterocyclic compound by reducing an N-heteraromatic compound including a central ring having 5 to 20 carbon atoms and a sp 2 hybridized nitrogen atom while simultaneously introducing a silyl group into a beta-position with respect to a nitrogen atom of the N-heteroaromatic compound, using a silane compound, in the presence of an organoboron catalyst.

2. The method of claim 1 , wherein an N-heterocyclic compound represented by the following Chemical Formula 1-1 is prepared by reacting a quinoline compound represented by the following Chemical Formula 2-1 with a silane compound represented by the following Chemical Formula 3-1, in the presence of the organoboron catalyst:

in Chemical Formulas 1-1, 2-1, and 3-1,
R 1 to R 7 are each independently hydrogen, (C1-C10)alkyl, (C1-C10)alkoxy, (C6-C12)aryl, halogen or (C6-C12)aryloxy, or the R 4 to R 7 may be each independently linked to an adjacent substituent via (C3-C12)alkenylene with or without a fused ring to form a monocyclic or polycyclic aromatic ring, and the alkyl, aryl and aryloxy of R 1 to R 7 may be further substituted with (C1-C10)alkyl;
R 8 and R 9 are each independently (C1-C10)alkyl or (C6-C12)aryl; and
R 10 is hydrogen or (C6-C12)aryl;
provided that R 8 , R 9 and R 10 are not (C6-C12)aryl at the same time.

3. The method of claim 1 , wherein an N-heterocyclic compound represented by the following Chemical Formula 1-2 is prepared by reacting an isoquinoline compound represented by the following Chemical Formula 2-2 with a silane compound represented by the following Chemical Formula 3-1, in the presence of the organoboron catalyst:

in Chemical Formulas 1-2, 2-2, and 3-1,
R 1 to R 7 are each independently hydrogen, (C1-C10)alkyl, (C1-C10)alkoxy, (C6-C12)aryl, halogen or (C6-C12)aryloxy, or the R 4 to R 7 may be each independently linked to an adjacent substituent via (C3-C12)alkenylene with or without a fused ring to form a monocyclic or polycyclic aromatic ring, and the alkyl, aryl and aryloxy of R 1 to R 7 may be further substituted with (C1-C10)alkyl;
R 8 and R 9 are each independently (C1-C10)alkyl or (C6-C12)aryl; and
R 10 is hydrogen or (C6-C12)aryl;
provided that R 8 , R 9 and R 10 are not (C6-C12)aryl at the same time.

4. The method of claim 1 , wherein an N-heterocyclic compound represented by the following Chemical Formula 1-3 is prepared by reacting a pyridine compound represented by the following Chemical Formula 2-3 with a silane compound represented by the following Chemical Formula 3-1, in the presence of the organoboron catalyst:

in Chemical Formulas 1-3, 2-3, and 3-1,
R 11 to R 15 are each independently hydrogen, (C1-C10)alkyl, (C1-C10)alkoxy, (C6-C12)aryl, halogen or (C6-C12)aryloxy, and the alkyl, aryl and aryloxy of R 11 to R 15 may be further substituted with (C1-C10)alkyl;
R 8 and R 9 are each independently (C1-C10)alkyl or (C6-C12)aryl; and
R 10 is hydrogen or (C6-C12)aryl;
provided that R 8 , R 9 and R 10 are not (C6-C12)aryl at the same time.

5. The method of claim 1 , wherein the organoboron catalyst is B(C 6 F 5 ) 3 or B(C 6 F 5 ) 2 Ar, and the Ar is (C6-C12)aryl.

6. The method of claim 1 , wherein the organoboron catalyst is used at 0.1 to 5.0 mol % based on 1 mol of the N-heteroaromatic compound.

7. The method of claim 6 , wherein the organoboron catalyst is used at 1.0 to 5.0 mol % based on 1 mol of the N-heteroaromatic compound.

8. The method of claim 1 , wherein the silane compound is used in amounts of 4 to 8 mol based on 1 mol of the N-heteroaromatic compound.

9. The method of claim 1 , wherein the silylative-reduction is performed at a reaction temperature of 23 to 100° C.

10. The method of claim 1 , wherein the silylative-reduction is performed by using one or two or more solvents selected from the group consisting of chloroform, dichloromethane, toluene, chlorobenzene, benzene, hexane and dichloroethane.

Assignees

• Inst Basic Science
• Korea Advanced Inst Sci & Tech

Inventors

• Chang Sukbok
• Park Sehoon
• Gandhamsetty Narasimhulu
• Joung Seewon
• Park Sung-Woo

Classifications

• C07F7/0829 Primary

  Hydrosilylation reactions · CPC title

• C07F7/0874

  Reactions involving a bond of the Si-O-Si linkage · CPC title

• C07F7/0836

  Compounds with one or more Si-OH or Si-O-metal linkage · CPC title

• C07F7/0896 Primary

  Compounds with a Si-H linkage · CPC title

• B01J31/14

  of aluminium or boron · CPC title