IP Library Granted Patent US 8,455,493
Granted Patent B2
US 8,455,493 · App. 12/632,140 · Granted Jun 4, 2013

Imidazopyrazine Syk inhibitors

Inventors: Scott A. Mitchell (East Haven, CT); Kevin S. Currie (North Branford, CT); Peter A. Blomgren (North Branford, CT); Jeffrey E. Kropf (Branford, CT); Seung H. Lee (Branford, CT); Jianjun Xu (Madison, CT); Douglas G. Stafford (Niskayuna, NY); James P. Harding (Loudonville, NY); Antonio J. M. Barbosa, Jr. (Bonita Springs, FL); Zhongdong Zhao (Guilford, CT); Soumya Mitra (Liverpool, NY); David M. Armistead (Sudbury, MA)
Assignee: Gilead Connecticut, Inc.
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Quick Facts
Patent No.
US 8,455,493
App. No.
12/632,140
Granted
Jun 4, 2013
Kind
B2
Abstract

Certain imidazopyrazines of Formula (I) and pharmaceutical compositions thereof are provided herein. Methods of treating patients suffering from certain diseases and disorders responsive to the inhibition of Syk activity, which comprises administering to such patients an amount of at least one chemical entity effective to reduce signs or symptoms of the disease or disorder are provided. Also provided are methods for determining the presence or absence of Syk kinase in a sample.

Claims (25)

1. At least one chemical entity chosen from compounds of Formula (I):

and pharmaceutically acceptable salts thereof, wherein

R 1 is chosen from (1-hydroxycyclobutyl)phenyl, (1,1,1-trifluoro-2-hydroxypropan-2-yl)phenyl, (2,2,2-trifluoro-1-hydroxyethyl)phenyl, (2-hydroxy-2-methylpropoxy)-3-methoxyphenyl, (2-hydroxyethyl)(methyl)amino)-3-methoxyphenyl, (2-methoxyethyl)(methyl)amino)-3-methoxyphenyl, (1-hydroxyethyl)phenyl, 3,4-dimethoxyphenyl, 3-methoxyphenyl, 4-ethoxy-3-methoxyphenyl, 4-hydroxymethyl-3-methoxyphenyl, 3-hydroxymethyl-4-methoxyphenyl, 2-fluoro-4-methoxyphenyl, 4-(dimethylamino)propoxy-3-methoxyphenyl, 4-hydroxypropoxy-3-methoxyphenyl, 4-(2-hydroxy-1,1-dimethylethyl)phenyl, 4-(1-hydroxy-l-methylethyl)phenyl, 4-methoxy-3-(pyrrolidin-1-yl)phenyl, 3-methoxy-4-(pyrrolidin-1-yl)phenyl, 3-methoxy-4-(propan-2-yloxy)phenyl, 3-methoxy-4-(morpholin-4-yl)phenyl, 4-(pyrrolidin-1-yl)phenyl, 4-(3-hydroxypyrrolidinyl)phenyl, 4-(4-hydroxypiperidinyl)-3-methoxyphenyl, 4-(3-hydroxyazetidinyl)-3-methoxyphenyl, 4-(3-hydroxypyrrolidinyl)-3-methoxyphenyl, 4-(2-methoxypropan-2-yl)phenyl, 4-(4-ethylpiperazin-1-yl)-3-methoxyphenyl, 4-(4-ethylpiperazin-1-yl)phenyl, 4-(3-hydroxy-3-methylpiperidinyl)phenyl, 3-hydroxymethylphenyl, and 4-(morpholin-4-yl)phenyl, or

R 1 is

wherein A is chosen from aryl, cycloalkyl and heterocycloalkyl groups, each of which groups having from 5 to 7 ring atoms including the atoms shared with the 6 membered aromatic ring and each of which groups being optionally substituted with one or more substituents independently chosen from —R a , —OR b , —O(C 1 -C 2 alkyl)O-, —SR b , guanidine, guanidine wherein one or more of the guanidine hydrogens are replaced with a lower-alkyl group, —NR b R c , halo, cyano, nitro, —COR b , —CO 2 R b , —CONR b R c , —OCOR b , —OCO 2 R a , —OCONR b R c , —NR c COR b , —NR c CO 2 R a , —NR c CONR b R c , —SOR a , —SO 2 R a , —SO 2 NR b R c , and —NR c SO 2 R a ;

wherein, for each occurrence,

R a is independently chosen from optionally substituted C 1 -C 6 alkyl, optionally substituted aryl, and optionally substituted heteroaryl;

R b is independently chosen from H, optionally substituted C 1 -C 6 alkyl, optionally substituted aryl, and optionally substituted heteroaryl; and

R c is independently chosen from hydrogen and optionally substituted C 1 -C 4 alkyl; or

R b and R c , and the nitrogen to which they are attached, form an optionally substituted heterocycloalkyl group; and

where each optionally substituted group of R a , R b , and R c is unsubstituted or independently substituted with one or more substituents independently selected from C 1 -C 4 alkyl, aryl, heteroaryl, aryl-C 1 -C 4 alkyl-, heteroaryl-C 1 -C 4 alkyl-, C 1 -C 4 haloalkyl-, —OC 1 -C 4 alkyl, —OC 1 -C 4 alkylphenyl, —C 1 -C 4 alkyl-OH, —OC 1 -C 4 haloalkyl, halo, —OH, —NH 2 , —C 1 -C 4 alkyl-NH 2 , —N(C 1 -C 4 alkyl)(C 1 -C 4 alkyl), —NH(C 1 -C 4 alkyl), —N(C 1 -C 4 alkyl)(C 1 -C 4 alkylphenyl), —NH(C 1 -C 4 alkylphenyl), cyano, nitro, oxo (as a substitutent for heteroaryl), —CO 2 H, —C(O)OC 1 -C 4 alkyl, —CON(C 1 -C 4 alkyl)(C 1 -C 4 alkyl), —CONH(C 1 -C 4 alkyl), —CONH 2 , —NHC(O)(C 1 -C 4 alkyl), —NHC(O)(phenyl), —N(C 1 -C 4 alkyl)C(O)(C 1 -C 4 alkyl), —N(C 1 -C 4 alkyl)C(O)(phenyl), —C(O)C 1 -C 4 alkyl, —C(0)C 1 -C 4 phenyl, —C(O)C 1 -C 4 haloalkyl, —OC(O)C 1 -C 4 alkyl, —SO 2 (C 1 -C 4 alkyl), —SO 2 (phenyl), —SO 2 (C 1 -C 4 haloalkyl), —SO 2 NH 2 , —SO 2 NH(C 1 -C 4 alkyl), —SO 2 NH(phenyl), —NHSO 2 (C 1 -C 4 alkyl), —NHSO 2 (phenyl), and —NHSO 2 (C 1 -C 4 haloalkyl);

R 2 is chosen from 1,3-benzoxazol-5-yl, 2-aminoquinazolin-6-yl, 2-hydroxyethyl-2H -indazol-6-yl, 1-hydroxyethyl-2H-indazol-6-yl, 1H-indazol-7-yl, 3-(diethylamino)methyl-1H -indazol-6-yl, 1,2-dihydroquinoxalin-2-on-6-yl, 1,2-dihydroquinolin-2-on-6-yl, 2 methyl-1,3-benzothiazol-5-yl, 3-(1,3- thiazol-4-ylmethylidene)-2,3-dihydro-1H -indol-2-on-6-yl, 1-methyl-1H-indazol-6-yl, (N,N-dimethylaminocarbonyl)indol-6-yl, 1,3-benzothiazol-5-yl, 1,3-benzothiazol-6-yl, 3-ethyl-1H-indazol-6-yl, 1H-indol-2-yl, 1H-indol-3-yl, 4-fluoro-1H-indazol-6-yl, 1H-1,2,3-benzotriazol-6-yl, 1H-1,3-benzodiazol-6-yl, 1H-indol-6-yl, 1H -pyrrolo [3,2-b]pyridin-6-yl, 1-methyl- 1H- 1,3-benzodiazol-5-yl, 1-methyl- 1H- 1,3-benzodiazol-6-yl, 1-methyl- 1H-benzo[d]imidazol-5-yl, 2-methyl- 1H-benzo[d]imidazol-5-yl, 3-amino- 1H-indazol-5-yl, 3-amino-1H-indazol-6-yl, 3-carbamoyl-1H-indazol-6-yl, 3-methyl-1H-indazol-6-yl, 5-fluoro-1H-indazol-6-yl, 1H-indazol-5-yl, 1H-indazol-6-yl, 3-amino-1H-indazol-5-yl, 1-methyl-1H-indazol-5-yl, 1-methyl-1H-indazol-6-yl, 3-methyl-1H-indazol-5-yl, 2,3-dimethyl-2H-indazol-5-yl, 3-amino-1H-indazol-5-yl, quinolin-6-yl, 2-aminoquinolin-6-yl, 3-aminoquinolin-6-yl, 2-aminoquinazolin-6-yl, 1H-1,2,3-benzotriazol-6-yl, 1H-imidazo[4,5-b]pyridin-6-yl, 1,3-benzoxazol-6-yl, 1H-indol-5-yl, 2-amino- 1H- 1,3-benzodiazol-6-yl, 2H,3H,4H-pyrido[3,2-b] [1,4] oxazin-3-on-6-yl, 1H,2H,3H -pyrido [3,2-h] [1,4] oxazin-3- on-6- yl, 4-b enzox azin-3- on-6- yl, 2-methyl-3,4-dihydro-2H- 1,4-benzoxazin-3-on-6-yl, 2-hydroxyquinolin-6-yl, and quinoxalin-2-o1-7-yl;

R 3 is chosen from hydrogen, lower alkyl, and halo;

R 4 is chosen from hydrogen and lower alkyl; and

R 5 is hydrogen.

2. At least one chemical entity of claim 1 , wherein R 1 is chosen from (1-hydroxyethyl)phenyl, 3,4-dimethoxyphenyl, 3-methoxyphenyl, 4-ethoxy-3-methoxyphenyl, 4-hydroxymethyl-3-methoxyphenyl, 3-hydroxymethyl-4-methoxyphenyl, 2-fluoro-4-methoxyphenyl, 4-(dimethylamino)propoxy-3-methoxyphenyl, 4-hydroxypropoxy-3-methoxyphenyl, 4-(2-hydroxy-1,1-dimethylethyl)phenyl, 4-(1-hydroxy-l-methylethyl)phenyl, 4-methoxy-3-(pyrrolidin-l-yl)phenyl, 3-methoxy-4-(pyrrolidin-l-yl)phenyl, 3-methoxy-4-(propan-2-yloxy)phenyl, 3-methoxy-4-(morpholin-4-yl)phenyl, 4-(pyrrolidin-l-yl)phenyl, 4-(3-hydroxypyrrolidinyl)phenyl, 4-(4-hydroxypiperidinyl)-3-methoxyphenyl, 4-(3-hydroxyazetidinyl)-3-methoxyphenyl, 4-(3-hydroxypyrrolidinyl)-3-methoxyphenyl, 4-(2-methoxypropan-2-yl)phenyl, 4-(4-ethylpiperazin-l-yl)-3-methoxyphenyl, 4-(4-ethylpiperazin-l-yl)phenyl, 4-(3-hydroxy-3-methylpiperidinyl)phenyl, 3-(hydroxymethyl)phenyl, and 4-(morpholin-4-yl)phenyl.

3. At least one chemical entity of claim 1 , wherein R 1 is

4. At least one chemical entity of claim 1 , wherein R 3 is chosen from hydrogen, methyl, ethyl, and chloro.

5. At least one chemical entity of claim 4 , wherein R 3 is hydrogen.

6. At least one chemical entity of claim 1 , wherein R 4 is chosen from hydrogen and methyl.

7. At least one chemical entity of claim 6 , wherein R 4 is hydrogen.

8. A pharmaceutical composition comprising at least one chemical entity of claim 1 , together with at least one pharmaceutically acceptable vehicle chosen from carriers, adjuvants, and excipients.

9. A compound chosen from

and pharmaceutically acceptable salts thereof.

10. A pharmaceutical composition comprising at least one chemical entity of claim 9 , together with at least one pharmaceutically acceptable vehicle chosen from carriers, adjuvants, and excipients.

Assignments (7)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 30, 2020
From: GILEAD CONNECTICUT, INC.
To: KRONOS BIO, INC.
Reel/Frame 053927/0969 →
MERGER AND CHANGE OF NAME Recorded Sep 17, 2020
From: COUGAR MERGER SUB, INC.; CGI PHARMACEUTICALS, INC.; CGI PHARMACEUTICALS, INC.
To: GILEAD CONNECTICUT, INC.
Reel/Frame 053799/0190 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 21, 2012
From: MITRA, SOUMYA
To: GILEAD CONNECTICUT, INC.
Reel/Frame 028820/0282 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 27, 2011
From: ARMISTEAD, DAVID M.
To: GILEAD CONNECTICUT, INC.
Reel/Frame 026655/0912 →
AGREEMENT AND PLAN OF MERGER Recorded Oct 4, 2010
From: CGI PHARMACEUTICALS, INC.
To: GILEAD CONNECTICUT, INC.
Reel/Frame 025084/0218 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 21, 2010
From: BARBOSA, ANTONIO J, JR.; ZHAO, ZHONGDONG
To: CGI PHARAMACEUTICALS, INC.
Reel/Frame 024425/0223 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 10, 2010
From: MITCHELL, SCOTT A.; CURRIE, KEVIN S.; BLOMGREN, PETER A.; KROPF, JEFFREY E.; LEE, SEUNG H.; XU, JIANJUN; STAFFORD, DOUGLAS G.; HARDING, JAMES P.
To: CGI PHARMACEUTICALS, INC.
Reel/Frame 023922/0796 →
Continuity (4)
Provisional Application 61120587 · Dec 8, 2008
Provisional Application 61140514 · Dec 23, 2008
Provisional Application 61240979 · Sep 9, 2009
Related Publication 20100222323A1 · Sep 2, 2010