IP Library Granted Patent US 9,624,224
Granted Patent B2
US 9,624,224 · App. 14/500,897 · Granted Apr 18, 2017

Inhibitors of Bruton's tyrosine kinase

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Quick Facts
Patent No.
US 9,624,224
App. No.
14/500,897
Granted
Apr 18, 2017
Kind
B2
Abstract

Disclosed herein are compounds that form covalent bonds with Bruton's tyrosine kinase (Btk). Also described are irreversible inhibitors of Btk. In addition, reversible inhibitors of Btk are also described. Also disclosed are pharmaceutical compositions that include the compounds. Methods of using the Btk inhibitors are disclosed, alone or in combination with other therapeutic agents, for the treatment of autoimmune diseases or conditions, heteroimmune diseases or conditions, cancer, including lymphoma, and inflammatory diseases or conditions.

Claims (82)

1. A compound of Formula (I) having the structure:

wherein:

L 1 is —N(R 2 )C(O)— or —C(O)N(R 2 )—;

R 1 is C 3 -C 12 heteroaryl, wherein C 3 -C 12 heteroaryl is optionally substituted with at least one R 3 ;

R 2 is H or C 1 -C 4 alkyl;

R 3 is halogen, —CF 3 , —CN, —NO 2 , —OR 6 , —N(R 6 )(R 7 ), substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 3 -C 6 cycloalkyl, or substituted or unsubstituted C 1 -C 6 heteroalkyl;

R 4 is H, substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 1 -C 6 heteroalkyl, substituted or unsubstituted C 3 -C 8 cycloalkyl, or substituted or unsubstituted C 2 -C 9 heterocycloalkyl;

R 5 is substituted or unsubstituted C 3 -C 8 cycloalkyl, or substituted or unsubstituted C 2 -C 9 heterocycloalkyl; or R 4 and R 5 together with the nitrogen atom to which they are attached form a C 2 -C 9 heterocycloalkyl;

R 6 is H, substituted or unsubstituted C 1 -C 6 alkyl, or substituted or unsubstituted C 1 -C 6 heteroalkyl;

R 7 is H, substituted or unsubstituted C 1 -C 6 alkyl, or substituted or unsubstituted C 1 -C 6 heteroalkyl;

R 10 is halogen, substituted or unsubstituted C 1 -C 6 alkyl, or substituted or unsubstituted C 1 -C 6 alkoxy;

m is 1 or 2;

n is 0 or 1; and

p is 0, 1, or 2;

or a pharmaceutically acceptable salt, or pharmaceutically acceptable solvate thereof.

2. The compound of claim 1 , wherein L 1 is —C(O)N(R 2 )—.

3. The compound of claim 2 , wherein L 1 is —C(O)N(H)—.

4. The compound of claim 1 , wherein R 1 is C 3 -C 12 heteroaryl substituted with one R 3 .

5. The compound of claim 4 , wherein R 1 is pyridyl.

6. The compound of claim 4 , wherein R 1 is thiazolyl or oxazolyl.

7. The compound of claim 4 , wherein R 3 is CN, substituted or unsubstituted C 1 -C 6 alkyl, or substituted or unsubstituted C 3 -C 6 cycloalkyl.

8. The compound of claim 1 , wherein R 4 is H.

9. The compound of claim 1 , wherein R 4 is substituted or unsubstituted C 1 -C 6 alkyl.

10. The compound of claim 9 , wherein R 4 is —CH 3 .

11. The compound of claim 1 , wherein R 5 is substituted or unsubstituted C 3 -C 8 cycloalkyl.

12. The compound of claim 11 , wherein R 5 is cyclopropyl.

13. The compound of claim 1 , wherein m is 1.

14. The compound of claim 1 , wherein m is 2.

15. The compound of claim 1 , wherein n is 0.

16. The compound of claim 1 , wherein n is 1.

17. The compound of claim 1 , wherein p is 0.

18. A compound having the structure:

or a pharmaceutically acceptable salt, or pharmaceutically acceptable solvate thereof.

19. Any one of the compounds selected from:

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-methylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-(trifluoromethyl)pyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-propylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-ethylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-2-methoxy-N-(4-methylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(5-methylthiazol-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(5-cyclopropylthiazol-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(5-isopropylthiazol-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(5-ethylthiazol-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(5-propylthiazol-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(5-(trifluoromethyl)thiazol-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(5-cyanothiazol-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(thiazol-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(oxazol-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(pyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-cyanopyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-cyclopropylpyridin-2-yl)benzamide;

R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-isopropylpyridin-2-yl)benzamide;

4-(4-amino-1-((1,4 trans)-4-but-2-ynamidocyclohexyl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-(trifluoromethyl)pyridin-2-yl)benzamide;

4-(4-amino-1-((1,4 trans)-4-((E)-4-(cyclopropyl(methyl)amino)but-2-enamido)cyclohexyl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-(trifluoromethyl)pyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(methylamino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-(trifluoromethyl)pyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(methylamino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-methylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-methylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-(trifluoromethyl)pyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(dimethylamino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-methylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(dimethylamino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-(trifluoromethyl)pyridin-2-yl)benzamide;

4-(1-((1,4 trans)-4-acrylamidocyclohexyl)-4-amino-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-methylpyridin-2-yl)benzamide;

4-(4-amino-1-((1,4 trans)-4-((E)-4-(dimethylamino)but-2-enamido)cyclohexyl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-methylpyridin-2-yl)benzamide;

4-(4-amino-1-((1,4 trans)-4-((E)-4-(cyclopropyl(methyl)amino)but-2-enamido)cyclohexyl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-methylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(dimethylamino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(pyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(dimethylamino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-isopropylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(dimethylamino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-cyanopyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(dimethylamino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-propylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)piperidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(pyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)piperidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-methylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)piperidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-(trifluoromethyl)pyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)piperidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-propylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)piperidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-cyanopyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)piperidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-isopropylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(dimethylamino)but-2-enoyl)piperidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(pyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(dimethylamino)but-2-enoyl)piperidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-methylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(dimethylamino)but-2-enoyl)piperidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-(trifluoromethyl)pyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(dimethylamino)but-2-enoyl)piperidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-propylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(dimethylamino)but-2-enoyl)piperidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-isopropylpyridin-2-yl)benzamide;

(R,E)-4-(4-amino-1-(1-(4-(dimethylamino)but-2-enoyl)piperidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(4-cyanopyridin-2-yl)benzamide; and

(R,E)-4-(4-amino-1-(1-(4-(cyclopropyl(methyl)amino)but-2-enoyl)pyrrolidin-3-yl)-1H-pyrazolo[3,4-d]pyrimidin-3-yl)-N-(pyridin-2-yl)benzamide;

or a pharmaceutically acceptable salt, or pharmaceutically acceptable solvate thereof.

20. A pharmaceutical composition comprising a therapeutically effective amount of a compound of claim 1 , or a pharmaceutically acceptable salt, or pharmaceutically acceptable solvate thereof, and a pharmaceutically acceptable excipient.

Assignments (5)
CORRECTIVE ASSIGNMENT TO CORRECT THE CONVEYING PARTY DATA PREVIOUSLY RECORDED ON REEL 036126 FRAME 0368. ASSIGNOR(S) HEREBY CONFIRMS THE MERGER AND CHANGE OF NAME. Recorded May 18, 2016
From: PHARMACYCLICS, INC.; OXFORD AMHERST LLC
To: PHARMACYCLICS LLC
Reel/Frame 038742/0371 →
CORRECTIVE ASSIGNMENT TO CORRECT THE CONVEYING PARTY DATA PREVIOUSLY RECORDED ON REEL 036126 FRAME 0359. ASSIGNOR(S) HEREBY CONFIRMS THE MERGER. Recorded May 17, 2016
From: OXFORD AMHERST CORPORATION; PHARMACYCLICS, INC.
To: PHARMACYCLICS, INC.
Reel/Frame 038742/0064 →
MERGER Recorded Jul 16, 2015
From: OXFORD AMHERST CORPORATION
To: PHARMACYCLICS, INC.
Reel/Frame 036126/0359 →
MERGER AND CHANGE OF NAME Recorded Jul 16, 2015
From: PHARMACYCLICS, INC.; OXFORD AMHERST LLC
To: PHARMACYCLICS LLC
Reel/Frame 036126/0368 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 12, 2015
From: CHEN, WEI; WANG, LONGCHENG; JIA, ZHAOZHONG J.; LOURY, DAVID J.
To: PHARMACYCLICS, INC.
Reel/Frame 034685/0247 →