IP Library Granted Patent US 7,148,250
Granted Patent B2
US 7,148,250 · App. 10/500,319 · Granted Dec 12, 2006

Indoles as NAALADase inhibitors

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Quick Facts
Patent No.
US 7,148,250
App. No.
10/500,319
Granted
Dec 12, 2006
Kind
B2
Abstract

This invention relates to new compounds, pharmaceutical compositions and diagnostic kits comprising such compounds, and methods of using such compounds for inhibiting NAALADase enzyme activity, detecting diseases where NAALAdase levels are altered, effecting neuronal activity, effecting TGF-β activity, inhibiting angiogenesis, and treating glutamate abnormalities, neuropathy, pain, compulsive disorders, prostate diseases, cancers and glaucoma.

Claims (51)

1. A compound of formula I

or a pharmaceutically acceptable salts, hydrates or optical isomers of said compound, wherein:

A 1 , A 2 , A 3 and A 4 are independently hydrogen, C 1 –C 9 alkyl, C 2 –C 9 alkenyl, C 2 –C 9 alkynyl, aryl, heteroaryl, carbocycle, heterocycle, C 1 –C 9 alkoxy, C 2 –C 9 alkenyloxy, phenoxy, benzyloxy, hydroxy, halo, nitro, cyano, isocyano, —COOR 6 , —COR 6 , —NR 6 R 7 , —SR 6 , —SOR 6 , —SO 2 R 6 , —SO 2 (OR 6 ), —(C═O)NR 6 R 7 , —(C═O)NR 6 (CH 2 ) n COOH, —NR 6 (C═O)R 7 or —(CH 2 ) n COOH, or any adjacent two of A 1 , A 2 , A 3 and A 4 form with the benzene ring a fused ring that is saturated or unsaturated, aromatic or non-aromatic, and carbocyclic or heterocyclic, said heterocyclic ring containing 1 or 2 oxygen, nitrogen and/or sulfur heteroatom(s);

n is 1–3;

R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently hydrogen, carboxy, C 1 –C 9 alkyl, C 2 –C 9 alkenyl, C 2 –C 9 alkynyl, aryl, heteroaryl, carbocycle or heterocycle; and

said alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocycle, heterocycle, alkoxy, alkenyloxy, phenoxy, benzyloxy and fused ring are independently unsubstituted or substituted with one or more substituent(s).

2. The compound of claim 1 , wherein:

A 1 , A 2 , A 3 and A 4 are independently hydrogen or —COOH;

R 1 , R 2 , R 3 and R 4 are each hydrogen; and

R 5 is hydrogen, phenyl, benzyl or phenylethyl, wherein said phenyl, benzyl and phenylethyl are independently unsubstituted or substituted with one or more substituent(s).

3. The compound of claim 2 , wherein R 5 is benzyl substituted with one or more substituent(s) independently selected from the group consisting of carboxy, halo, C 1 –C 4 alkyl and C 1 –C 4 alkoxy.

4. The compound of claim 1 , wherein said compound is selected from the group consisting of:

3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

3-(2-mercaptoethyl)-1H-indole-2,7-dicarboxylic acid;

1-[(3-carboxyphenyl)methyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

1-[(2-bromo-5-carboxyphenyl)methyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

1-[(4-carboxyphenyl)methyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

3-(2-mercaptoethyl)-1-(phenylmethyl)-1H-indole-2-carboxylic acid;

1-[(2-carboxyphenyl)methyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

1-[[3-carboxy-5-(1,1-dimethylethyl)phenyl]methyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

1-[(4-bromo-3-carboxyphenyl)methyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

1-[(2-carboxy-5-methoxyphenyl)methyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

3-(2-mercaptoethyl)-1-phenyl-1H-indole-2-carboxylic acid;

3-(2-mercaptoethyl)-1-(2-phenylethyl)-1H-indole-2-carboxylic acid;

1-(3-carboxyphenyl)-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid; and

1-[3-carboxy-5-(1,1-dimethylethyl)phenyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid.

5. The compound of claim 1 , wherein said compound is an enantiomer or an enantiomer-enriched mixture.

6. A pharmaceutical composition comprising:

(i) an effective amount of a compound of claim 1 ; and

(ii) a pharmaceutically acceptable carrier.

7. The pharmaceutical composition of claim 6 , wherein said the compound of claim 1 is selected from the group consisting of:

3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

3-(2-mercaptoethyl)-1H-indole-2,7-dicarboxylic acid;

1-[(3-carboxyphenyl)methyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

1-[(2-bromo-5-carboxyphenyl)methyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

1-[(4-carboxyphenyl)methyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

3-(2-mercaptoethyl)-1-(phenylmethyl)-1H-indole-2-carboxylic acid;

1-[(2-carboxyphenyl)methyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

1-[[3-carboxy-5-(1,1-dimethylethyl)phenyl]methyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

1-[(4-bromo-3-carboxyphenyl)methyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

1-[(2-carboxy-5-methoxyphenyl)methyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid;

3-(2-mercaptoethyl)-1-phenyl-1H-indole-2-carboxylic acid;

3-(2-mercaptoethyl)-1-(2-phenylethyl)-1H-indole-2-carboxylic acid;

1-(3-carboxyphenyl)-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid; and

1-[3-carboxy-5-(1,1-dimethylethyl)phenyl]-3-(2-mercaptoethyl)-1H-indole-2-carboxylic acid.

8. The pharmaceutical composition of claim 6 , wherein:

A 1 , A 2 , A 3 and A 4 are independently hydrogen or —COOH;

R 1 , R 2 , R 3 and R 4 are each hydrogen; and

R 5 is hydrogen, phenyl, benzyl or phenylethyl, wherein said phenyl, benzyl or phenylethyl are independently substituted with one or more substituent(s).

9. The pharmaceutical composition of claim 8 , wherein R 5 is benzyl substituted with one or more substituent(s) independently selected from the group consisting of carboxy, halo, C 1 –C 4 alkyl and C 1 –C 4 alkoxy.

10. The pharmaceutical composition of claim 6 , wherein the compound is an enantiomer or an enantiomer-enriched mixture.

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 24, 2009
From: EISAI CORPORATION OF NORTH AMERICA
To: EISAI INC.
Reel/Frame 023699/0188 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 19, 2009
From: MGI GP, INC.
To: EISAI CORPORATION OF NORTH AMERICA
Reel/Frame 022277/0779 →
CERTIFICATE OF MERGER OF GRANITE ACQUISITION, INC. WITH AND INTO GUILFORD PHARMACEUTICALS INC. Recorded Dec 23, 2008
From: GRANITE ACQUISITION, INC.; GUILFORD PHARMACEUTICALS INC.
To: MGI GP, INC.
Reel/Frame 022024/0105 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 22, 2004
From: TSUKAMOTO, TAKASHI; GRELLA, BRIAN; MAJER, PAVEL
To: GUILFORD PHARMACEUTICALS INC.
Reel/Frame 016012/0092 →