Chiral phase-transfer catalyst and method for preparing alpha-amino acid by using the same

Patent metadata

Field	Value
Publication number	US-10696621-B2
Application number	US-201716302618-A
Country	US
Kind code	B2
Filing date	Feb 6, 2017
Priority date	May 19, 2016
Publication date	Jun 30, 2020
Grant date	Jun 30, 2020

Abstract

The present invention relates to a novel chiral phase-transfer catalyst, and a method for preparing an alpha-amino acid by using the same. According to the present invention, an alpha-amino acid of high optical purity could be synthesized in a high yield under an easy industrially applicable reaction condition by using a novel cinchona alkaloid compound as a chiral phase-transfer catalyst, and thus the present invention can be used as a key technique of the asymmetric alpha-amino acid synthesis and preparation field.

First claim

What is claimed is:

1. A cinchona-alkaloid compound of Formula 1 below:

wherein,
X is selected from the group consisting of —CH 2 —, —C(OH)H—, —C(═O)—, —O—, —S—, and —S(═O)—;
R is

R 1 is selected from the group consisting of hydrogen, C 1 to C 10 alkyl, and
C 1 to C 5 alkoxy;
R 2 is vinyl or ethyl;
R 3 is selected from the group consisting of hydrogen, C 1 to C 10 alkyl, allyl, C 5 to C 10 aryl, naphthalen-1-yl-methyl, and anthracen-9-yl-methyl; and
Y − is selected from the group consisting of: halogen anion of fluoride, chloride, bromide, and iodide, IO 4 − , ClO 4 − , R 4 SO 3 − , trifluoromethane sulfonate (OTf − ) and HSO 4 − , wherein R 4 is C 1 -C 4 alkyl or C 5 -C 0 aryl.

2. The compound according to claim 1 , wherein said X of the compound of Formula 1 is one of —CH 2 —, —C(OH)H— or —C(═O)—, wherein
R 1 is hydrogen or C 1 to C 5 alkoxy;
R 2 is vinyl or ethyl;
R 3 is hydrogen, C 1 to C 10 alkyl, allyl, or C 5 to C 10 aryl; and
Y − is halogen anion selected from the group consisting of fluorine, chlorine, bromine, and iodine.

3. The compound according to claim 1 , wherein said X of the compound of Formula 1 is —CH 2 —, —C(OH)H— or —C(═O)—, wherein
R 1 is hydrogen or methoxy group;
R 2 is vinyl or ethyl group;
R 3 is hydrogen or allyl group; and
Y − is halogen anion selected from the group consisting of fluoride, chloride, bromide, and iodide.

4. The compound according to claim 3 , wherein said compound is selected from the group consisting of:
4,4′-bis(cinchonidium-N-methyl)biphenyl methanone dibromide;
4,4′-bis(O(9)-allylcinchonidium-N-methyl)biphenyl methanone dibromide;
4,4′-bis(hydrocinchonidium-N-methyl)biphenyl methanone dibromide;
4,4′-bis(O(9)-allylhydrocinchonidium-N-methyl)biphenyl methanone dibromide;
3,4′-bis(cinchonidium-N-methyl)biphenyl methanone dibromide;
3,4′-bis(O(9)-allylcinchonidium-N-methyl)biphenyl methanone dibromide;
3,3′-bis(cinchonidium-N-methyl)biphenyl methanone dibromide;
3,3′-bis(O(9)-allylcinchonidium-N-methyl)biphenyl methanone dibromide;
4,4′-bis(cinchonidium-N-methyl)biphenyl methane dibromide;
4,4′-bis(O(9)-allylcinchonidium-N-methyl)biphenyl methane dibromide;
4,4′-bis(hydrocinchonidium-N-methyl)biphenyl methane dibromide,
4,4′-bis(O(9)-allylhydrocinchonidium-N-methyl)biphenyl methane dibromide;
4,4′-bis(quinium-N-methyl)biphenyl methane dibromide;
4,4′-bis(O(9)-allylquinium-N-methyl)biphenyl methane dibromide;
4,4′-bis(cinchonidium-N-methyl)biphenyl methanol dibromide;
4,4′-bis(O(9)-allylcinchonidium-N-methyl)biphenyl methanol dibromide,
4,4′-bis(hydrocinchonidium-N-methyl)biphenyl methanol dibromide;
4,4′-bis(O(9)-allylhydrocinchonidium-N-methyl)biphenyl methanol dibromide,
4,4′-bis(cinchonium-N-methyl)biphenyl methanone dibromide,
4,4′-bis(O(9)-allylcinchonium-N-methyl)biphenyl methanone dibromide,
4,4′-bis(cinchonium-N-methyl)biphenyl methane dibromide,
4,4′-bis(O(9)-allylcinchonium-N-methyl)biphenyl methane dibromide;
4,4′-bis(quinidium-N-methyl)biphenyl methane dibromide;
4,4′-bis(O(9)-allylquinidium-N-methyl)biphenyl methane dibromide;
4,4′-bis(cinchonium-N-methyl)biphenyl methanol dibromide; and
4,4′-bis(O(9)-allylcinchonium-N-methyl)biphenyl methanol dibromide.

5. The compound according to claim 1 , wherein said X of the compound of Formula 1 is —O—, —S— or —S(═O)—, wherein
R 1 is hydrogen or C 1 -C 5 alkoxy;
R 2 is vinyl or ethyl;
R 3 is hydrogen, C 1 -C 10 alkyl, allyl, or C 5 -C 10 aryl; and
Y − is halogen anion selected from the group consisting of fluorine, chlorine, bromine, and iodine.

6. The compound according to claim 1 , wherein said X of the compound of Formula 1 is —O—, —S— or —S(═O)—, wherein
R 1 is hydrogen or methoxy;
R 2 is vinyl or ethyl;
R 3 is hydrogen, allyl, or benzyl; and
Y − is halogen anion selected from the group consisting of fluorine, chlorine, bromine, and iodine.

7. The compound according to claim 6 , wherein said compound is selected from the group consisting of:
4,4′-bis(cinchonidium-N-methyl)biphenyl ether dibromide;
4,4′-bis(O(9)-allylcinchonidium-N-methyl)biphenyl ether dibromide;
4,4′-bis(O(9)-benzyl-cinchonidium-N-methyl)biphenyl ether dibromide;
4,4′-bis(hydrocinchonidium-N-methyl)biphenyl ether dibromide;
4,4′-bis(O(9)-allylhydrocinchonidium-N-methyl)biphenyl ether dibromide;
4,4′-bis(quinium-N-methyl)biphenyl ether dibromide;
4,4′-bis(O(9)-allylquinium-N-methyl)biphenyl ether dibromide;
3,3′-bis(cinchonidium-N-methyl)biphenyl ether dibromide;
3,3′-bis(O(9)-allylcinchonidium-N-methyl)biphenyl ether dibromide;
4,4′-bis(cinchonidium-N-methyl)biphenyl thioether dibromide;
4,4′-bis(O(9)-allylcinchonidium-N-methyl)biphenyl thioether dibromide;
4,4′-bis(hydrocinchonidium-N-methyl)biphenyl thioether dibromide;
4,4′-bis(O(9)-allylhydrocinchonidium-N-methyl)biphenyl thioether dibromide;
4,4′-bis(quinium-N-methyl)biphenyl thioether dibromide;
4,4′-bis(O(9)-allylquinium-N-methyl)biphenyl thioether dibromide;
3,3′-bis(cinchonidium-N-methyl)biphenyl sulfide dibromide;
3,3′-bis(O(9)-allylcinchonidium-N-methyl)biphenyl sulfide dibromide;
4,4′-bis(cinchonidium-N-methyl)biphenyl sulfoxide dibromide;
4,4′-bis(O(9)-allylcinchonidium-N-methyl)biphenyl sulfoxide dibromide;
4,4′-bis(hydrocinchonidium-N-methyl)biphenyl sulfoxide dibromide;
4,4′-bis(O(9)-allylhydrocinchonidium-N-methyl)biphenyl sulfoxide dibromide;
4,4′-bis(cinchonium-N-methyl)biphenyl ether dibromide;
4,4′-bis(O(9)-allylcinchonium-N-methyl)biphenyl ether dibromide;
4,4′-bis(quinidium-N-methyl)biphenyl ether dibromide;
4,4′-bis(O(9)-allylquinidium-N-methyl)biphenyl ether dibromide;
4,4′-bis(cinchonium-N-methyl)biphenyl thioether dibromide;
4,4′-bis(O(9)-allylcinchonium-N-methyl)biphenyl thioether dibromide;
4,4′-bis(quinidium-N-methyl)biphenyl thioether dibromide;
4,4′-bis(cinchonium-N-methyl)biphenyl sulfoxide dibromide; and
4,4′-bis(O(9)-allylcinchonium-N-methyl)biphenyl sulfoxide dibromide.

Assignees

• Univ Yeungnam Res Cooperation Foundation

Inventors

• Nahm Kee Pyung
• Lee Yeon Ji
• Lim Bae Geun
• Woo Seung A
• Oh Ji Inn
• Son Won Gyoung

Classifications

• B01J31/0239 Primary

  Quaternary ammonium compounds · CPC title

• C07D453/04 Primary

  having a quinolyl-4, a substituted quinolyl-4 or a alkylenedioxy-quinolyl-4 radical linked through only one carbon atom, attached in position 2, e.g. quinine · CPC title

• B01J31/02

  containing organic compounds or metal hydrides · CPC title

• B01J2231/4205

  C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type · CPC title

• C07D471/04

  Ortho-condensed systems · CPC title