IP Library Granted Patent US 9,540,385
Granted Patent B2
US 9,540,385 · App. 14/708,099 · Granted Jan 10, 2017

Pyrrolopyrimidine compounds as kinase inhibitors

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Quick Facts
Patent No.
US 9,540,385
App. No.
14/708,099
Granted
Jan 10, 2017
Kind
B2
Abstract

Disclosed herein are pyrrolo[2,3-d]pyrimidine 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 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 (63)

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

wherein:

R 1 is halogen, —CN, —OH, —NH 2 , —SH, substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 1 -C 4 alkoxy, substituted or unsubstituted C 1 -C 6 heteroalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted heteroaryl or substituted or unsubstituted C 3 -C 8 cycloalkyl;

G is substituted or unsubstituted C 2 -C 4 alkenyl, substituted or unsubstituted C 2 -C 4 alkynyl, substituted or unsubstituted C 3 -C 8 cycloalkyl, substituted or unsubstituted C 1 -C 4 alkoxy, substituted or unsubstituted C 1 -C 4 heteroalkyl, substituted or unsubstituted C 2 -C 7 heterocycloalkyl, halogen, —CN, —NO 2 , —OH, —OCF 3 , —OCH 2 F, —OCF 2 H, —CF 3 , —SCH 3 , —N(R 21 )S(═O) 2 R 23 , S(═O) 2 N(R 21 )(R 22 ), —S(═O)R 23 , —S(═O) 2 R 23 , —C(═O)R 23 , —OC(═O)R 23 , —CO 2 R 21 , N(R 21 )(R 22 ), —C(═O)N(R 21 )(R 22 ), —N(R 21 )C(═O)R 23 , N(R 21 )C(═O)OR 22 , N(R 21 )C(═O)N(R 21 )(R 22 ), or L a -Ar;

L a is a bond, —CH 2 —, —CH(OH)—, —C(O)—, —CH 2 O—, —OCH 2 —, —SCH 2 , —CH 2 S—, —N(R 21 )—, —N(R 21 )C(O)—, —C(O)N(R 21 )—, —N(R 21 )C(O)N(R 21 )—, —O—, —S—, —S(O)—, —S(O) 2 —, —N(R 21 )S(O) 2 —, or —S(O) 2 N(R 21 )—;

Ar is a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl;

each R 24 is independently halogen, —CN, —NO 2 , —OH, —OCF 3 , —OCH 2 F, —OCF 2 H, —CF 3 , —SCH 3 , —N(R 21 )S(═O) 2 R 23 , S(═O) 2 N(R 21 )(R 22 ), —S(═O)R 23 , —S(═O) 2 R 23 , —C(═O)R 23 , —OC(═O)R 23 , —CO 2 R 21 , N(R 21 )(R 22 ), —C(═O)N(R 21 )(R 22 ), —N(R 21 )C(═O)R 23 , N(R 21 )C(═O)OR 22 , N(R 21 )C(═O)N(R 21 )(R 22 ), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heterocycloalkyl, or substituted or unsubstituted cycloalkyl;

each R 21 and R 22 is independently H, substituted or unsubstituted C 1 -C 6 alkyl, or substituted or unsubstituted C 3 -C 8 cycloalkyl;

each R 23 is each independently substituted or unsubstituted C 1 -C 6 alkyl, or substituted or unsubstituted C 3 -C 8 cycloalkyl;

n is 0-4;

Y is an optionally substituted group selected from among C 1 -C 6 alkylene, C 1 -C 6 heteroalkylene, C 6 -C 12 arylene, C 3 -C 12 heteroarylene, C 1 -C 6 alkyleneC 6 -C 12 arylene, C 1 -C 6 alkyleneC 3 -C 12 heteroarylene, C 1 -C 6 alkyleneC 3 -C 8 cycloalkylene, C 1 -C 6 alkyleneC 2 -C 7 heterocycloalkylene, C 3 -C 8 cycloalkylene, C 2 -C 7 heterocycloalkylene, fused C 3 -C 8 cycloalkyleneC 2 -C 7 heterocycloalkylene, and spiro C 3 -C 8 cycloalkyleneC 2 -C 7 heterocycloalkylene;

Z is —C(═O)—, —N(R a )C(═O)—, or —N(R a )S(═O) x —, where x is 1 or 2, and R a is H, substituted or unsubstituted C 1 -C 6 alkyl, or substituted or unsubstituted C 3 -C 8 cycloalkyl;

R 6 is H or L-J-W;

R 7 and R 8 are independently H or L-J-W; or R 7 and R 8 taken together form a bond;

L and J are each independently a bond, substituted or unsubstituted C 1 -C 6 alkylene, substituted or unsubstituted C 3 -C 8 cycloalkylene, substituted or unsubstituted C 1 -C 6 heteroalkylene, substituted or unsubstituted C 2 -C 7 heterocycloalkylene, substituted or unsubstituted C 6 -C 12 arylene, substituted or unsubstituted C 3 -C 12 heteroarylene, —CO—, —O—, or —S—;

W is H, or NR 25 R 26 ; and

R 25 and R 26 are each independently H, substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 3 -C 8 cycloalkyl, substituted or unsubstituted C 1 -C 6 heteroalkyl, substituted or unsubstituted C 2 -C 7 heterocycloalkyl, substituted or unsubstituted C 6 -C 12 aryl, or substituted or unsubstituted C 3 -C 12 heteroaryl; or

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

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

wherein:

R 1 is halogen, —CN, —OH, —NH 2 , —SH, substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 1 -C 4 alkoxy, substituted or unsubstituted C 1 -C 6 heteroalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted heteroaryl or substituted or unsubstituted C 3 -C 8 cycloalkyl;

G is substituted or unsubstituted C 2 -C 4 alkenyl, substituted or unsubstituted C 2 -C 4 alkynyl, substituted or unsubstituted C 3 -C 8 cycloalkyl, unsubstituted C 1 -C 4 alkoxy, unsubstituted C 1 -C 4 heteroalkyl, substituted or unsubstituted C 2 -C 7 heterocycloalkyl, halogen, —CN, —NO 2 , —OH, —OCF 3 , —OCH 2 F, —OCF 2 H, —CF 3 , —SCH 3 , —N(R 21 )S(═O) 2 R 23 , S(═O) 2 N(R 21 )(R 22 ), —S(═O)R 23 , —S(═O) 2 R 23 , —C(═O)R 23 , —OC(═O)R 23 , —CO 2 R 21 , N(R 21 )(R 22 ), —C(═O)N(R 21 )(R 22 ), —N(R 21 )C(═O)R 23 , N(R 21 )C(═O)OR 22 , N(R 21 )C(═O)N(R 21 )(R 22 ), or L a -Ar;

L a is a bond, —CH 2 —, —CH(OH)—, —C(O)—, —CH 2 O—, —SCH 2 , —CH 2 S—, —N(R 21 )—, —N(R 21 )C(O)—, —C(O)N(R 21 )—, —N(R 21 )C(O)N(R 21 )—, —O—, —S—, —S(O)—, —S(O) 2 —, —N(R 21 )S(O) 2 —, or —S(O) 2 N(R 21 )—;

Ar is a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl;

each R 24 is independently halogen, —CN, —NO 2 , —OH, —OCF 3 , —OCH 2 F, —OCF 2 H, —CF 3 , —SCH 3 , —N(R 21 )S(═O) 2 R 23 , S(═O) 2 N(R 21 )(R 22 ), —S(═O)R 23 , —S(═O) 2 R 23 , —C(═O)R 23 , —OC(═O)R 23 , —CO 2 R 21 , N(R 21 )(R 22 ), —C(═O)N(R 21 )(R 22 ), —N(R 21 )C(═O)R 23 , N(R 21 )C(═O)OR 22 , N(R 21 )C(═O)N(R 21 )(R 22 ), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heterocycloalkyl, or substituted or unsubstituted cycloalkyl;

each R 21 and R 22 is independently H, substituted or unsubstituted C 1 -C 6 alkyl, or substituted or unsubstituted C 3 -C 8 cycloalkyl;

each R 23 is each independently substituted or unsubstituted C 1 -C 6 alkyl, or substituted or unsubstituted C 3 -C 8 cycloalkyl;

n is 0-4;

Y is an optionally substituted group selected from among C 1 -C 6 alkylene, C 1 -C 6 heteroalkylene, C 6 -C 12 arylene, C 3 -C 12 heteroarylene, C 1 -C 6 alkyleneC 6 -C 12 arylene, C 1 -C 6 alkyleneC 3 -C 12 heteroarylene, C 1 -C 6 alkyleneC 3 -C 8 cycloalkylene, C 1 -C 6 alkyleneC 2 -C 7 heterocycloalkylene, C 3 -C 8 cycloalkylene, C 2 -C 7 heterocycloalkylene, fused C 3 -C 8 cycloalkyleneC 2 -C 7 heterocycloalkylene, and spiro C 3 -C 8 cycloalkyleneC 2 -C 7 heterocycloalkylene;

Z is —C(═O)—, —N(R a )C(═O)—, —S(═O) x —, or —N(R a )S(═O) x —, where x is 1 or 2, and R a is H, substituted or unsubstituted C 1 -C 6 alkyl, or substituted or unsubstituted C 3 -C 8 cycloalkyl;

R 6 is H or L-J-W;

R 7 and R 8 are independently H or L-J-W; or R 7 and R 8 taken together form a bond;

L and J are each independently a bond, substituted or unsubstituted C 1 -C 6 alkylene, substituted or unsubstituted C 3 -C 8 cycloalkylene, substituted or unsubstituted C 1 -C 6 heteroalkylene, substituted or unsubstituted C 2 -C 7 heterocycloalkylene, substituted or unsubstituted C 6 -C 12 arylene, substituted or unsubstituted C 3 -C 12 heteroarylene, —CO—, —O—, or —S—;

W is H, or NR 25 R 26 ; and

R 25 and R 26 are each independently H, substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 3 —C cycloalkyl, substituted or unsubstituted C 1 -C 6 heteroalkyl, substituted or unsubstituted C 2 -C 7 heterocycloalkyl, substituted or unsubstituted C 6 -C 12 aryl, or substituted or unsubstituted C 3 -C 12 heteroaryl; or

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

3. The compound of one of claim 1 or 2 , wherein G is L a -Ar.

4. The compound of claim 3 , wherein L a is —O—; and Ar is phenyl.

5. The compound of claim 4 , wherein Y is C 2 -C 7 heterocycloalkylene.

6. The compound of claim 5 , wherein Z is —C(═O)—.

7. The compound of claim 6 , wherein R 6 , R 7 , and R 8 are each H.

8. The compound of claim 6 , wherein R 6 and R 8 are H; and R 7 is L-J-W.

9. The compound of claim 8 , wherein L is a bond, substituted or unsubstituted C 1 -C 6 alkylene, or substituted or unsubstituted C 3 -C 8 cycloalkylene; and J is a bond, substituted or unsubstituted C 1 -C 6 alkylene, substituted or unsubstituted C 3 -C 8 cycloalkylene, substituted or unsubstituted C 1 -C 6 heteroalkylene, substituted or unsubstituted C 2 -C 7 heterocycloalkylene, substituted or unsubstituted C 6 -C 12 arylene, or substituted or unsubstituted C 3 -C 12 heteroarylene.

10. The compound of claim 9 , wherein L is a bond; J is —CH 2 —; and W is NR 25 R 26 .

11. The compound of claim 10 , wherein R 25 is H, substituted or unsubstituted C 1 -C 6 alkyl, or substituted or unsubstituted C 3 -C 8 cycloalkyl; and R 26 is substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 3 -C 8 cycloalkyl, substituted or unsubstituted C 1 -C 6 heteroalkyl, substituted or unsubstituted C 2 -C 7 heterocycloalkyl, substituted or unsubstituted C 6 -C 12 aryl, or substituted or unsubstituted C 3 -C 12 heteroaryl.

12. The compound of claim 11 , wherein R 25 and R 26 are each CH 3 .

13. The compound of claim 11 , wherein R 25 is CH 3 and R 26 is cyclopropyl.

14. The compound of claim 4 , wherein Y is phenyl.

15. The compound of claim 14 , wherein Z is —C(═O)—, —NHC(═O)—, or —N(CH 3 )C(═O)—.

16. The compound of claim 15 , wherein R 6 , R 7 , and R 8 are each H.

17. The compound of claim 15 , wherein R 6 and R 8 are H; and R 7 is L-J-W.

18. The compound of claim 17 , wherein L is a bond, substituted or unsubstituted C 1 -C 6 alkylene, or substituted or unsubstituted C 3 -C 8 cycloalkylene; and J is a bond, substituted or unsubstituted C 1 -C 6 alkylene, substituted or unsubstituted C 3 -C 8 cycloalkylene, substituted or unsubstituted C 1 -C 6 heteroalkylene, substituted or unsubstituted C 2 -C 7 heterocycloalkylene, substituted or unsubstituted C 6 -C 12 arylene, or substituted or unsubstituted C 3 -C 12 heteroarylene.

19. The compound of claim 18 , wherein L is a bond; J is —CH 2 —; and W is —NR 25 R 26 .

20. The compound of claim 19 , wherein R 25 is H, substituted or unsubstituted C 1 -C 6 alkyl, or substituted or unsubstituted C 3 -C 8 cycloalkyl; and R 26 is substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 3 -C 8 cycloalkyl, substituted or unsubstituted C 1 -C 6 heteroalkyl, substituted or unsubstituted C 2 -C 7 heterocycloalkyl, substituted or unsubstituted C 6 -C 12 aryl, or substituted or unsubstituted C 3 -C 12 heteroaryl.

21. The compound of claim 20 , wherein R 25 and R 26 are each —CH 3 .

22. The compound of claim 20 , wherein R 25 is CH 3 and R 26 is cyclopropyl.

23. The compound of one of claim 1 or 2 , wherein n is 0.

24. The compound of one of claim 1 or 2 , wherein R 1 is —F, —Cl, —CH 3 , or —OCH 3 .

25. Any one of the compounds selected from:

or a pharmaceutically acceptable solvate, or pharmaceutically acceptable salt thereof; wherein

R is methyl, —CN, fluoro, chloro, hydroxy, —NH 2 , or —CO 2 H; and

X is methyl, ethyl, propyl, isopropyl, cyclopropyl, tert-butyl, or trifluoromethyl.

26. A pharmaceutical composition comprising a pharmaceutically acceptable excipient and a compound of any one of claim 1 , 2 , or 25 .

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 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 8, 2016
From: CHEN, WEI; WANG, LONGCHENG; LOURY, DAVID J.
To: PHARMACYCLICS, INC.
Reel/Frame 037438/0668 →
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 →