IP Library Granted Patent US 11,453,676
Granted Patent B2
US 11,453,676 · App. 16/962,710 · Granted Sep 27, 2022

Inhibitors of protein arginine deiminases

Inventor: Toufike Kanouni (Rancho Santa Fe, CA)
Assignee: FORWARD THERAPEUTICS, INC.
C07D487/10C07D209/42C07D401/06C07D401/12C07D403/06C07D403/12C07D405/12C07D487/04
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Quick Facts
Patent No.
US 11,453,676
App. No.
16/962,710
Granted
Sep 27, 2022
Kind
B2
Abstract

Provided herein are inhibitors of protein arginine deiminases (PADs), pharmaceutical compositions comprising said the compounds, and methods for using the compounds for the treatment of diseases.

Claims (89)

1. A compound, or pharmaceutically acceptable salt or solvate thereof, having the structure of Formula (I):

wherein,

R 5 is selected from halogen;

R 6 is selected from fluoro;

R 7 is selected from fluoro;

X is selected from:

wherein n is 2, 3, or 4; each R 1 is independently selected from hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted cycloalkylalkyl; and each R 2 is independently hydrogen or optionally substituted alkyl;

wherein p is 1, 2, 3, or 4; q is 1, 2, 3, or 4; each R 1 is independently selected from hydrogen, halogen, —OH, —NH 2 , optionally substituted alkyl, or optionally substituted alkoxy; each R 2 is hydrogen or optionally substituted alkyl; and R 3 is hydrogen or optionally substituted alkyl;

wherein p is 1, 2, 3, or 4; q is 1, 2, 3, or 4; each R 1 is independently selected from hydrogen, halogen, —OH, —NH 2 , optionally substituted alkyl, or optionally substituted alkoxy; each R 2 is hydrogen or optionally substituted alkyl; and R 3 is hydrogen or optionally substituted alkyl.

2. The compound of claim 1 , or pharmaceutically acceptable salt or solvate thereof, wherein X is:

wherein n is 2, 3, or 4; each R 1 is independently selected from hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted cycloalkylalkyl; and each R 2 is independently hydrogen or optionally substituted alkyl.

3. The compound of claim 2 , or pharmaceutically acceptable salt or solvate thereof, wherein each R 1 is independently selected from hydrogen, optionally substituted alkyl; each R 2 is hydrogen; and n is 2 or 3.

4. The compound of claim 1 , or pharmaceutically acceptable salt or solvate thereof, wherein X is:

wherein p is 1, 2, 3, or 4; q is 1, 2, 3, or 4; each R 1 is independently selected from hydrogen, halogen, —OH, —NH 2 , optionally substituted alkyl, or optionally substituted alkoxy; each R 2 is hydrogen or optionally substituted alkyl; and R 3 is hydrogen or optionally substituted alkyl.

5. The compound of claim 4 , or pharmaceutically acceptable salt or solvate thereof, wherein R 2 is hydrogen, and R 3 is hydrogen.

6. The compound of claim 4 , or pharmaceutically acceptable salt or solvate thereof, wherein each R 1 is independently selected from hydrogen or optionally substituted alkyl.

7. The compound of claim 4 , or pharmaceutically acceptable salt or solvate thereof, wherein p is 2, and q is 1.

8. The compound of claim 4 , or pharmaceutically acceptable salt or solvate thereof, wherein X is 3-amino-4-hydroxypyrrolidin-1-yl.

9. The compound of claim 1 , or pharmaceutically acceptable salt or solvate thereof, wherein X is:

wherein p is 1, 2, 3, or 4; q is 1, 2, 3, or 4; each R 1 is independently selected from hydrogen, halogen, —OH, —NH 2 , optionally substituted alkyl, or optionally substituted alkoxy; each R 2 is hydrogen or optionally substituted alkyl; and R 3 is hydrogen or optionally substituted alkyl.

10. The compound of claim 9 , or pharmaceutically acceptable salt or solvate thereof, wherein R 2 is hydrogen, R 3 is hydrogen, p is 2, q is 1, and each R 1 is independently selected from hydrogen or optionally substituted alkyl.

11. The compound of claim 1 , or pharmaceutically acceptable salt or solvate thereof, wherein R 5 is chloro, R 6 is fluoro, and R 7 is fluoro.

12. A compound, or pharmaceutically acceptable salt or solvate thereof, selected from:

(R)-(3-Aminopyrrolidin-1-yl)(5-chloro-6,7-difluoro-1H-indol-2-yl)methanone,

(R)-(3-Aminopyrrolidin-1-yl)(5,6,7-trifluoro-1H-indol-2-yl)methanone,

(R)-(3-Aminopyrrolidin-1-yl)(5-bromo-6,7-difluoro-1H-indol-2-yl)methanone,

((3 S,4R)-3-Amino-4-fluoro-pyrrolidin-1-yl)-(5-chloro-6,7-difluoro-1H-indol-2-yl)-methanone,

(S)-N-(1-Aminopropan-2-yl)-5-chloro-6,7-difluoro-1H-indole-2-carboxamide,

(S)-N-(1-Aminobutan-2-yl)-5-chloro-6,7-difluoro-1H-indole-2-carboxamide,

N-(2-Amino-1-cyclopropylethyl)-5-chloro-6,7-difluoro-1H-indole-2-carboxamide,

N-(3-(Aminomethyl)oxetan-3-yl)-5-chloro-6,7-difluoro-1H-indole-2-carboxamide,

5-Chloro-6,7-difluoro-N-((3 S,4R)-4-methylpyrrolidin-3-yl)-1H-indole-2-carboxamide,

5-Chloro-6,7-difluoro-N-((3 S,4S)-4-methylpyrrolidin-3-yl)-1H-indole-2-carboxamide,

5-Chloro-6,7-difluoro-N-((3R,4R)-4-hydroxypyrrolidin-3-yl)-1H-indole-2-carboxamide,

5-Chloro-6,7-difluoro-N-((3R,4S)-4-hydroxypyrrolidin-3-yl)-1H-indole-2-carboxamide,

5-Chloro-6,7-difluoro-N-((3 S,4R)-4-hydroxypyrrolidin-3-yl)-1H-indole-2-carboxamide,

5-Chloro-6,7-difluoro-N-((3 S,4S)-4-hydroxypyrrolidin-3-yl)-1H-indole-2-carboxamide,

(S)-N-(1-Amino-4-methylpentan-2-yl)-5-chloro-6,7-difluoro-1H-indole-2-carboxamide,

5-Chloro-6,7-difluoro-N-((3R,4R)-4-methylpyrrolidin-3-yl)-1H-indole-2-carboxamide,

(R)-N-(1-Aminopropan-2-yl)-5-chloro-6,7-difluoro-1H-indole-2-carboxamide, ((3 S,4S)-3-Amino-4-hydroxypyrrolidin-1-yl)(5-chloro-6,7-difluoro-1H-indol-2-yl)methanone,

N-(Azetidin-3-yl)-5-chloro-6,7-difluoro-1H-indole-2-carboxamide,

(3-Aminoazetidin-1-yl)(5-chloro-6,7-difluoro-1H-indol-2-yl)methanone,

(R)-5-Chloro-6,7-difluoro-N-(pyrrolidin-3-yl)-1H-indole-2-carboxamide,

(S)-5-Chloro-6,7-difluoro-N-(pyrrolidin-3-yl)-1H-indole-2-carboxamide,

(S)-(3-Aminopyrrolidin-1-yl)(5-chloro-6,7-difluoro-1H-indol-2-yl)methanone,

(S)-N-(1-Amino-3,3-dimethylbutan-2-yl)-5-chloro-6,7-difluoro-1H-indole-2-carboxamide,

(5-Chloro-6,7-difluoro-1H-indol-2-yl)((3 S,4S)-3,4-diaminopyrrolidin-1-yl)methanone,

N-((3 S,4S)-4-Aminopyrrolidin-3-yl)-5-chloro-6,7-difluoro-1H-indole-2-carboxamide,

N-((3R,4S)-4-Aminopyrrolidin-3-yl)-5-chloro-6,7-difluoro-1H-indole-2-carboxamide,

((3 S,4R)-3-Amino-4-hydroxypyrrolidin-1-yl)(5-chloro-6,7-difluoro-1H-indol-2-yl)methanone,

5-Chloro-6,7-difluoro-N-((3 S,4S)-4-methoxypyrrolidin-3-yl)-1H-indole-2-carboxamide,

5-Chloro-6,7-difluoro-N-((3R,4R)-4-methoxypyrrolidin-3-yl)-1H-indole-2-carboxamide,

((3 S,4S)-3-Amino-4-methoxypyrrolidin-1-yl)(5-chloro-6,7-difluoro-1H-indol-2-yl)methanone,

5-Chloro-6,7-difluoro-N-((3R,4 S)-4-methylpyrrolidin-3-yl)-1H-indole-2-carboxamide,

((3 S,4S)-3-Amino-4-fluoropyrrolidin-1-yl)(5-chloro-6,7-difluoro-1H-indol-2-yl)methanone,

(R)-(3-Aminopiperidin-1-yl)(5-chloro-6,7-difluoro-1H-indol-2-yl)methanone,

(S)-5-Chloro-6,7-difluoro-N-(piperidin-3-yl)-1H-indole-2-carboxamide,

(R)-5-Chloro-6,7-difluoro-N-(piperidin-3-yl)-1H-indole-2-carboxamide,

5-Chloro-6,7-difluoro-N-((3R,4 S)-4-methylpiperidin-3-yl)-1H-indole-2-carboxamide,

((3 S,4S)-3-Amino-4-fluoropiperidin-1-yl)(5-chloro-6,7-difluoro-1H-indol-2-yl)methanone, and

((3 S,4R)-3-Amino-4-fluoropiperidin-1-yl)(5-chloro-6,7-difluoro-1H-indol-2-yl)methanone.

13. A compound, or pharmaceutically acceptable salt or solvate thereof, selected from:

(S)-5-chloro-6,7-difluoro-N-methyl-N-(pyrrolidin-3-yl)-1H-indole-2-carboxamide,

N-(azetidin-3-yl)-5-chloro-6,7-difluoro-N-methyl-1H-indole-2-carboxamide,

5-chloro-6,7-difluoro-N-(3-methylazetidin-3-yl)-1H-indole-2-carboxamide,

5-chloro-6,7-difluoro-N-((2 S, 3 S)-2-methylazetidin-3-yl)-1H-indole-2-carboxamide,

5-chloro-6,7-difluoro-N-((2R,3R)-2-methylazetidin-3-yl)-1H-indole-2-carboxamide,

(1R,5S)-3,6-diazabicyclo[3.2.0]heptan-6-yl(5-chloro-6,7-difluoro-1H-indol-2-yl)methanone,

(5-chloro-6,7-difluoro-1H-indol-2-yl)((3aS,6aS)-hexahydropyrrolo[3,4-b]pyrrol-1(2H)-yl)methanone,

(5-chloro-6,7-difluoro-1H-indol-2-yl)((3aR,6aR)-hexahydropyrrolo[3,4-b]pyrrol-1(2H)-yl)methanone,

(5-chloro-6,7-difluoro-1H-indol-2-yl)((3aR,6aS)-hexahydropyrrolo[3,4-c]pyrrol-2(1H)-yl)methanone,

(5-chloro-6,7-difluoro-1H-indol-2-yl)(2,6-diazaspiro[3.3]heptan-2-yl)methanone,

(5-chloro-6,7-difluoro-1H-indol-2-yl)(2,6-diazaspiro[3.4]octan-2-yl)methanone,

(S)-5-chloro-6,7-difluoro-N-(pyrrolidin-3-ylmethyl)-1H-indole-2-carboxamide,

(R)-5-chloro-6,7-difluoro-N-(pyrrolidin-3-ylmethyl)-1H-indole-2-carboxamide,

(S)-N-(1-aminopropan-2-yl)-5-chloro-6,7-difluoro-N-methyl-1H-indole-2-carboxamide,

((3 S,4S)-3-amino-4-hydroxypyrrolidin-1-yl)(5-bromo-6,7-difluoro-1H-indol-2-yl)methanone,

((3 S,4S)-3-amino-4-hydroxypyrrolidin-1-yl)(6,7-difluoro-5-iodo-1H-indol-2-yl)methanone, and

((3 S,4R)-3-amino-4-hydroxypyrrolidin-1-yl)(5-bromo-6,7-difluoro-1H-indol-2-yl)methanone.

14. The compound of claim 12 , or pharmaceutically acceptable salt or solvate thereof, wherein the compound is selected from:

(S)-N-(1-Aminopropan-2-yl)-5-chloro-6,7-difluoro-1H-indole-2-carboxamide; or

5-Chloro-6,7-difluoro-N-((3 S,4S)-4-methylpyrrolidin-3-yl)-1H-indole-2-carboxamide.

15. The compound of claim 12 , or pharmaceutically acceptable salt or solvate thereof, wherein the compound is selected from:

((3 S,4S)-3-Amino-4-hydroxypyrrolidin-1-yl)(5-chloro-6,7-difluoro-1H-indol-2-yl)methanone; or

((3 S,4R)-3-Amino-4-hydroxypyrrolidin-1-yl)(5-chloro-6,7-difluoro-1H-indol-2-yl)methanone.

16. The compound of claim 13 , or pharmaceutically acceptable salt or solvate thereof, wherein the compound is selected from:

((3 S,4S)-3-amino-4-hydroxypyrrolidin-1-yl)(5-bromo-6,7-difluoro-1H-indol-2-yl)methanone; or

((3 S,4R)-3-amino-4-hydroxypyrrolidin-1-yl)(5-bromo-6,7-difluoro-1H-indol-2-yl)methanone.

17. A pharmaceutical composition comprising a compound of Formula (I), or pharmaceutically acceptable salt or solvate thereof, as described in claim 1 , and at least one pharmaceutically acceptable excipient.

Assignments (2)
CHANGE OF NAME Recorded Jul 7, 2022
From: PADFORWARD LLC
To: FORWARD THERAPEUTICS, INC.
Reel/Frame 060614/0154 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 5, 2021
From: KANOUNI, TOUFIKE
To: PADFORWARD LLC
Reel/Frame 057703/0186 →
Continuity (2)
Provisional Application 62625899 · Feb 2, 2018
Related Publication 20210053975A1 · Feb 25, 2021