IP Library Granted Patent US 9,938,260
Granted Patent B2
US 9,938,260 · App. 15/509,895 · Granted Apr 10, 2018

Soluble guanylate cyclase activators and their use

Inventors: Nerina Dodic (Les Ulis, FR); Anne Marie Jeanne Bouillot (Les Ulis, FR)
Assignee: GlaxoSmithKline Intellectual Property Development Limited
C07D405/14C07D401/14
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Quick Facts
Patent No.
US 9,938,260
App. No.
15/509,895
Granted
Apr 10, 2018
Kind
B2
Abstract

The invention relates to activators of soluble guanylate cyclase and their use in pharmaceutical compositions, primarily topically administered ophthalmic compositions. The pharmaceutical compositions are useful for reducing intraocular pressure in animals of the mammalian species.

Claims (88)

1. A compound according to formula (I):

or a pharmaceutically acceptable salt thereof, wherein:

wherein:

R 1 is selected from H and —C 1-3 alkyl;

R 2 and R 3 are each independently selected from H and halogen;

R 4 is selected from H, —C 1-3 alkyl, —O—C 1-3 alkyl, —O—C 3-4 cycloalkyl, —O—(CH 2 ) p -oxetanyl, and —O—(CH 2 ) p -tetrahydrofuranyl;

X and Y are each CH; or if X is N, then Y is CH; or if Y is N then X is CH;

A is absent or O;

R 5 is selected from —C 1-4 alkyl, —C 3-4 cycloalkyl, —(CH 2 ) n CN, —(CH 2 ) n CF 3 , —(CH 2 ) m -tetrahydrofuranyl, —(CH 2 ) m -oxetanyl, —C 2-5 alkyl-OH, —C 2-5 alkyl-OCH 3 and —CO—R 6 ;

R 6 is selected from —C 1-6 alkyl and —C 3-6 cycloalkyl, optionally substituted by —OH, —OCH 3 , —CN, COOH or —F, or R 6 is —(CH 2 ) m -tetrahydrofuranyl or —(CH 2 ) m -oxetanyl, or R6 is a (CH 2 ) m -4 to 5-membered heterocycle;

n is 1 or 2;

m is 0 or 1; and

p is 0 or 1.

2. A compound, or a pharmaceutically acceptable salt thereof, which is:

1-(6-(2-((4-(1-(cyanomethyl)piperidin-4-yl)-2-methylbenzyl)oxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(2,2,2-trifluoroethyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(oxetane-3-carbonyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((4-methyl-6-(1-(2,2,2-trifluoroethyl)piperidin-4-yl)pyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(2-((6-(1-(cyanomethyl)piperidin-4-yl)-4-methylpyridin-3-yl)methoxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-(2-methyl-6-(1-(2,2,2-trifluoroethyl)piperidin-4-yl)pyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((2-methyl-6-(1-(oxetan-3-yl)piperidin-4-yl)pyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((2-methyl-6-(1-(tetrahydrofuran-3-yl)piperidin-4-yl)pyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((2-methyl-6-(1-((tetrahydrofuran-3-yl)methyl)piperidin-4-yl)pyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(2-((6-(1-(cyanomethyl)piperidin-4-yl)-2-methylpyridin-3-yl)methoxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((2-methyl-6-(1-(oxetane-3-carbonyl)piperidin-4-yl)pyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((6-(1-(2-hydroxyacetyl)piperidin-4-yl)-2-methylpyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3-chloro-2-((2-methyl-4-(1-(oxetan-3-yl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(oxetan-3-yl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(tetrahydrofuran-3-yl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(2-((4-(1-cyclopropylpiperidin-4-yl)-2-methylbenzyl)oxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((4-(1-(2-methoxyethyl)piperidin-4-yl)-2-methylbenzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((4-(1-(2-hydroxyethyl)piperidin-4-yl)-2-methylbenzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(3,3,3-trifluoropropyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((4-(1-(2-hydroxyacetyl)piperidin-4-yl)-2-methylbenzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((4-(1-(2-methoxyacetyl)piperidin-4-yl)-2-methylbenzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(2-((4-(1-(2-cyanoacetyl)piperidin-4-yl)-2-methylbenzyl)oxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(2-((4-(1-(2-cyclopropylacetyl)piperidin-4-yl)-2-methylbenzyl)oxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(tetrahydrofuran-3-carbonyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

(S)-1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(tetrahydrofuran-3-carbonyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine -4-carboxylic acid;

(R)-1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(tetrahydrofuran-3-carbonyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(2-(oxetan-3-yl)acetyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(2-(tetrahydrofuran-3-yl)acetyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(2-((4-(1-(2-carboxyacetyl)piperidin-4-yl)-2-methylbenzyl)oxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(2-((4-(1-(2-(1H-1,2,4-triazol-1-yl)acetyl)piperidin-4-yl)-2-methylbenzyl)oxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((2-methoxy-4-(1-(2,2,2-trifluoroethyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid;

1-(6-(3,5-difluoro-2-((2-(oxetan-3-yloxy)-4-(1-(2,2,2-trifluoroethyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid; or

1-(6-(3,5-difluoro-2-((2-methyl-4-((1-(2,2,2-trifluoroethyl)piperidin-4-yl)oxy)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid.

3. A pharmaceutical composition comprising a compound, or a pharmaceutically acceptable salt thereof, according to claim 1 and one or more pharmaceutically acceptable excipients.

4. A compound which is 1-(6-(3,5-difluoro-2-((4-methyl-6-(1-(2,2,2-trifluoroethyl)piperidin-4-yl)pyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, sodium salt.

5. A compound which is 1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(tetrahydrofuran-3-carbonyppiperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, sodium salt.

6. A compound which is 1-(6-(3,5-difluoro-2-((4-methyl-6-(1-(2,2,2-trifluoroethyl)piperidin-4-yl)pyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, or a pharmaceutically acceptable salt thereof.

7. A compound which is 1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(tetrahydrofuran-3-carbonyppiperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, or a pharmaceutically acceptable salt thereof.

8. A compound which is 1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(2,2,2-trifluoroethyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid.

9. A compound which is 1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(2,2,2-trifluoroethyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, sodium salt.

10. A compound which is:

1-(6-(2-((4-(1-(cyanomethyl)piperidin-4-yl)-2-methylbenzyl)oxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(2,2,2-trifluoroethyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(oxetane-3-carbonyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((4-methyl-6-(1-(2,2,2-trifluoroethyl)piperidin-4-yl)pyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(2-((6-(1-(cyanomethyl)piperidin-4-yl)-4-methylpyridin-3-yl)methoxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((2-methyl-6-(1-(2,2,2-trifluoroethyl)piperidin-4-yl)pyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((2-methyl-6-(1-(oxetan-3-yl)piperidin-4-yl)pyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((2-methyl-6-(1-(tetrahydrofuran-3-yl)piperidin-4-yl)pyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((2-methyl-6-(1-((tetrahydrofuran-3-yl)methyl)piperidin-4-yl)pyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(2-((6-(1-(cyanomethyl)piperidin-4-yl)-2-methylpyridin-3-yl)methoxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((2-methyl-6-(1-(oxetane-3-carbonyl)piperidin-4-yl)pyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((6-(1-(2-hydroxyacetyl)piperidin-4-yl)-2-methylpyridin-3-yl)methoxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3-chloro-2-((2-methyl-4-(1-(oxetan-3-yppiperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(oxetan-3-yl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(tetrahydrofuran-3-yl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(2-((4-(1-cyclopropylpiperidin-4-yl)-2-methylbenzyl)oxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((4-(1-(2-methoxyethyl)piperidin-4-yl)-2-methylbenzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((4-(1-(2-hydroxyethyppiperidin-4-yl)-2-methylbenzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(3,3,3-trifluoropropyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((4-(1-(2-hydroxyacetyl)piperidin-4-yl)-2-methylbenzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((4-(1-(2-methoxyacetyl)piperidin-4-yl)-2-methylbenzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(2-((4-(1-(2-cyanoacetyl)piperidin-4-yl)-2-methylbenzyl)oxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(2-((4-(1-(2-cyclopropylacetyl)piperidin-4-yl)-2-methylbenzyl)oxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(tetrahydrofuran-3-carbonyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

(S)-1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(tetrahydrofuran-3-carbonyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

(R)-1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(tetrahydrofuran-3-carbonyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((2-methyl-4-(1-(2-(oxetan-3-yl)acetyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-24(2-methyl-4-(1-(2-(tetrahydrofuran-3-yl)acetyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(2-((4-(1-(2-carboxyacetyl)piperidin-4-yl)-2-methylbenzyl)oxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid, di-Sodium salt;

1-(6-(2-((4-(1-(2-(1H-1,2,4-triazol-1-yl)acetyl)piperidin-4-yl)-2-methylbenzyl)oxy)-3,5-difluorophenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((2-methoxy-4-(1-(2,2,2-trifluoroethyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt;

1-(6-(3,5-difluoro-2-((2-(oxetan-3-yloxy)-4-(1-(2,2,2-trifluoroethyl)piperidin-4-yl)benzyl)oxy)phenyl)pyridin-2-yl)piperidine-4-carboxylic acid, Sodium salt; or

1-(6-(3,5-difluoro-2-((2-methyl-4-((1-(2,2,2-trifluoroethyl)piperidin-4-yl)oxy)benzyl)oxy)phenyl)pyridin-2-ylpiperidine-4carboxylic acid, Sodium salt.

Assignments (3)
CHANGE OF ADDRESS Recorded Oct 8, 2025
From: GLAXOSMITHKLINE INTELLECTUAL PROPERTY DEVELOPMENT LIMITED
To: GLAXOSMITHKLINE INTELLECTUAL PROPERTY DEVELOPMENT LIMITED
Reel/Frame 073032/0390 →
CORRECTIVE ASSIGNMENT TO CORRECT THE SECOND INVENTOR"S EXECUTION DATE PREVIOUSLY RECORDED AT REEL: 44311 FRAME: 245. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Jul 11, 2019
From: BOUILLOT, ANNE MARIE JEANNE; DODIC, NERINA
To: GLAXOSMITHKLINE INTELLECTUAL PROPERTY DEVELOPMENT LIMITED
Reel/Frame 049727/0373 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 6, 2017
From: BOUILLOT, ANNE MARIE JEANNE; DODIC, NERINA
To: GLAXOSMITHKLINE INTELLECTUAL PROPERTY DEVELOPMENT LIMITED
Reel/Frame 044311/0245 →
Continuity (2)
Provisional Application 62052537 · Sep 19, 2014
Related Publication 20170305888A1 · Oct 26, 2017