IP Library Granted Patent US 10,005,767
Granted Patent B2
US 10,005,767 · App. 15/419,660 · Granted Jun 26, 2018

Compositions and methods for inhibition of the JAK pathway

Inventors: Yan Chen (Foster City, CA); Vanessa Taylor (San Francisco, CA); Hui Li (Santa Clara, CA); Rajinder Singh (Belmont, CA)
Assignee: Rigel Pharmaceuticals, Inc.
C07D413/12A61K31/155A61K31/506A61K31/538A61K31/5377A61K31/5383A61K31/54A61K31/541A61K31/5415A61K31/55A61K31/551A61K31/635A61K31/675A61K45/06C07D401/14C07D403/12C07D413/04C07D413/14C07D419/14C07D451/02C07D471/04C07D471/08C07D487/04C07D487/08C07D487/10C07D491/08C07D498/04C07F9/65583
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Quick Facts
Patent No.
US 10,005,767
App. No.
15/419,660
Granted
Jun 26, 2018
Kind
B2
Abstract

Disclosed are compounds of formula I, compositions containing them, and methods of use for the compounds and compositions in the treatment of conditions in which modulation of the JAK pathway or inhibition of JAK kinases, particularly JAK 2 and JAK3, are therapeutically useful.

Claims (104)

1. A compound of formula I, or salt thereof,

wherein:

X and Y are each independently O, S, S(O), SO 2 or NR 1 ;

each R 1 is independently for each occurrence H, optionally substituted C 1-6 alkyl, C(O)—C 1-6 alkyl, CO 2 —C 1-6 alkyl or R 50 ;

each R 50 is —C(R 9 ) 2 -A-R 10 , where A is O or S; each R 9 is independently for each occurrence H, optionally substituted C 1-6 alkyl, optionally substituted C 6-10 aryl or optionally substituted C 7-16 arylalkyl; or alternatively, two R 9 , together with the carbon to which they are attached, form an optionally substituted C 3-8 cycloalkyl group or an optionally substituted 3-8 membered heteroalicyclyl; R 10 is R a or —P(O)(OR 11 ) 2 ; each R 11 is independently for each occurrence R a or a monovalent cationic group; or two R 11 , together with the atoms to which they are attached, form a 4-8 membered cyclic phosphate group, or two R 11 together represent a divalent cationic group;

ring A is bicyclic;

each R 2 is independently for each occurrence H, R e , R b , R e substituted with one or more of the same or different R a and/or R b , —OR e substituted with one or more of the same or different R a and/or R b , —SR e substituted with one or more of the same or different R a and/or R b , —C(O)R e substituted with one or more of the same or different R a and/or R b , —N(R a )R e where R e is substituted with one or more of the same or different R a and/or R b , —S(O) 2 Re substituted with one or more of the same or different R a and/or R b , —N(R a )—S(O) 2 R e where R e is substituted with one or more of the same or different R a and/or R b , —B(OR a ) 2 , —B(N(R c ) 2 ) 2 , —(C(R a ) 2 ) m —R b , —O—(C(R a ) 2 ) m —R b , —S—(C(R a ) 2 ) m —R b , —O—(C(R b ) 2 ) m —R a , —N(R a )—(C(R a ) 2 ) m —R b , —O—(CH 2 ) m —CH((CH 2 ) m R b )R b , —C(O)N(R a )—(C(R a ) 2 ) m —R b , —O—(C(R a ) 2 ) m —C(O)N(R a )—(C(R a ) 2 ) m —R b , —N((C(R a ) 2 ) m R b ) 2 , —S—(C(R a ) 2 ) m —C(O)N(R a )—(C(R a ) 2 ) m —R b , —N(R a )—C(O)—N(R a )—(C(R a ) 2 ) m —R b , —N(R a )—C(O)—(C(R a ) 2 ) m —C(R a )(R b ) 2 or —N(R a )—(C(R a ) 2 ) m —C(O)—N(R a )—(C(R a ) 2 ) m —R b ;

each R a is independently for each occurrence H, deuterium, C 1-6 alkyl, C 3-8 cycloalkyl, C 4-11 cycloalkylalkyl, C 6-10 aryl, C 7-16 arylalkyl, 2-6 membered heteroalkyl, 3-10 membered heteroalicyclyl, 4-11 membered heteroalicyclylalkyl, 5-15 membered heteroaryl or 6-16 membered heteroarylalkyl;

each R b is independently for each occurrence ═O, —OR a , —O—(C(R a ) 2 ) m —OR a , haloC 1-3 alkyloxy, ═S, —SR a , ═NR a , ═NOR a , —N(R c ) 2 , halo, —CF 3 , —CN, —NC, —OCN, —SCN, —NO, —NO 2 , ═N 2 , —N 3 , —S(O)R a , —S(O) 2 R a , —SO 3 R a , —S(O)N(R c ) 2 , —S(O) 2 N(R c ) 2 , —OS(O)R a , —OS(O) 2 R a , —OSO 3 R a , —OS(O) 2 N(R c ) 2 , —C(O)R a , —CO 2 R a , —C(O)N(R c ) 2 , —C(NR a )—N(R c ) 2 , —C(NOH)—R a , —C(NOH)—N(R c ) 2 , —OC(O)R a , —OC(O)OR a , —OC(O)N(R c ) 2 , —OC(NH)—N(R c ) 2 , —OC(NR a )—N(R c ) 2 , —N(R a )—S(O) 2 H, —[N(R a )C(O)] n R a , —[N(R a )C(O)] n OR a , —[N(R a )C(O)] n N(R c ) 2 or —[N(R a )C(NR a )] n —N(R c ) 2 ;

each R c is independently for each occurrence R a , or, alternatively, two R c are taken together with the nitrogen atom to which they are bonded to form a 3 to 10-membered heteroalicyclyl or a 5-10 membered heteroaryl which may optionally include one or more of the same or different additional heteroatoms and which is optionally substituted with one or more of the same or different R a and/or R d groups;

each R d is ═O, —OR a , haloC 1-3 alkyloxy, C 1-6 alkyl, ═S, —SR a , ═NR a , ═NOR a , —N(R a ) 2 , halo, —CF 3 , —CN, —NC, —OCN, —SCN, —NO, —NO 2 , ═N 2 , —N 3 , —S(O)R a , —S(O 2 )R a , —SO 3 R a , —S(O)N(R a ) 2 , —S(O) 2 N(R a ) 2 , —OS(O)R a , —OS(O) 2 R a , —OSO 3 R a , —OS(O) 2 N(R a ) 2 , —C(O)R a , —CO 2 R a , —C(O)N(R a ) 2 , —C(NR a )N(R a ) 2 , —C(NOH)R a , —C(NOH)N(R a ) 2 , —OCO 2 R a , —OC(O)N(R a ) 2 , —OC(NR a )N(R a ) 2 , —[N(R a )C(O)] n R a , —(C(R a ) 2 ) n —OR a , —N(R a )—S(O) 2 R a , —C(O)—C 1-6 haloalkyl, —S(O) 2 C 1-6 haloalkyl, —OC(O)R a , —O(C(R a ) 2 ) m —OR a , —S(C(R a ) 2 ) m —OR a , —N(R a )C 1-6 haloalkyl, —P(O)(OR a ) 2 , —N(R a )—(C(R a ) 2 ) m —OR a , —[N(R a )C(O)] n OR a , —[N(R a )C(O)] n N(R a ) 2 , —[N(R a )C(NR a )] n N(R a ) 2 or —N(R a )C(O)C 1-6 haloalkyl; or two R d , taken together with the atom or atoms to which they are attached, combine to form a 3-10 membered partially or fully saturated mono or bicyclic ring, optionally containing one or more heteroatoms and optionally substituted with one or more R a ;

each R e is independently for each occurrence C 1-6 alkyl, C 3-8 cycloalkyl, C 4-11 cycloalkylalkyl, C 6-10 aryl, C 7-16 arylalkyl, 2-6 membered heteroalkyl, 3-10 membered heteroalicyclyl, 4-11 membered heteroalicyclylalkyl, 5-15 membered heteroaryl or 6-16 membered heteroarylalkyl;

p is 0, 1, 2, 3 or 4;

each m is 1, 2 or 3;

each n is 0, 1, 2 or 3;

two R 2 groups, taken together with the atom or atoms to which they are attached, combine to form a 4-10 membered partially or fully saturated mono or bicyclic ring, optionally containing one or more heteroatoms and optionally substituted with one or more R a and/or R b ;

Z 1 and Z 2 are each independently CH, CR 2 or N;

R 3 is H, optionally substituted C 1-6 alkyl or R 50 ;

R 4 is H, optionally substituted C 1-6 alkyl or R 50 ; and

R 5 is halo, —CN, optionally substituted C 1-6 alkyl, alkynyl, hydroxy, optionally substituted C 1-6 alkoxy, nitro, —N(R a ) 2 , —C(O)N(R a ) 2 , —CO 2 R a or —C(O)R a .

2. The compound of claim 1 , or a salt thereof, wherein the A ring is bicyclic aryl or bicyclic heteroaryl.

3. The compound of claim 1 , or a salt thereof, having a formula IA3

wherein R b is OH, C 1-6 alkyl, —CO 2 C 1-6 alkyl, —C(O)C 1-6 alkyl or —S(O) 2 C 1-6 alkyl.

4. The compound of claim 1 , or a salt thereof, having a formula II

wherein:

ring B, together with the two phenyl ring atoms to which it is attached, forms a 5-, 6- or 7-membered ring, optionally comprising 1, 2 or 3 heteroatoms independently selected from N(R c ), O and S;

each R 1 independently is, for each occurrence, H, optionally substituted C 1-6 alkyl, C(O)—C 1-6 alkyl, CO 2 —C 1-6 alkyl or R 50 ;

each R 50 is —C(R 9 ) 2 -A-R 10 , where A is 0 or S; each R 9 is independently for each occurrence H, optionally substituted C 1-6 alkyl, optionally substituted C 6-10 aryl or optionally substituted C 7-16 arylalkyl; or alternatively, two R 9 , together with the carbon to which they are attached, form an optionally substituted C 3-8 cycloalkyl group or an optionally substituted 3-8 membered heteroalicyclyl; R 10 is R a or —P(O)(OR 11 ) 2 ; each R 11 is independently for each occurrence R a or a monovalent cationic group; or two R 11 , together with the atoms to which they are attached, form a 4-8 membered cyclic phosphate group, or two R 11 together represent a divalent cationic group

R 5 is halo, —CN, optionally substituted C 1-6 alkyl, alkynyl, hydroxy, optionally substituted C 1-6 alkoxy, nitro, —N(R a ) 2 , —C(O)N(R a ) 2 , —CO 2 R a or —C(O)R a

each R a independently is C 1-6 alkyl;

each R b independently is, for each occurrence, ═O, —OR a , haloC 1-3 alkyloxy, —SR a , —N(R c ) 2 , halo, —CF 3 , —CN, —S(O) 2 N(R c ) 2 , —S(O) 2 R a , —C(O)R a , —CO 2 R a , —C(O)N(R c ) 2 , —N(R a )—S(O) 2 H, or —C(R a ) 2 —N(R c ) 2 ; and

Z 1 is CH, CR 2 , C-halo or, C-optionally substituted C 1-6 alkyl, or N.

5. The compound of claim 4 wherein the B ring is cyclopentane, pyrrolidine, imidazolidine, 1,3-dioxolane, oxazolidine, tetrahydrofuran, cyclohexane, morpholine, piperidine, dioxane, oxathiazinane, piperazine, cycloheptane, cycloheptene, azepane, tetrahydroazepine, diazepane, cyclooctane, cyclooctene, azocane, hexahydroazocine, diazocane or hexahydrodiazocine.

6. The compound of claim 1 , or a salt thereof, having a formula IIa

wherein:

each R 1 independently is, for each occurrence, H, optionally substituted C 1-6 alkyl, C(O)—C 1-6 alkyl, CO 2 —C 1-6 alkyl or R 50 ;

each R 50 is —C(R 9 ) 2 -A-R 10 , where A is O or S; each R 9 is independently for each occurrence H, optionally substituted C 1-6 alkyl, optionally substituted C 6-10 aryl or optionally substituted C 7-16 arylalkyl; or alternatively, two R 9 , together with the carbon to which they are attached, form an optionally substituted C 3-8 cycloalkyl group or an optionally substituted 3-8 membered heteroalicyclyl; R 10 is R a or —P(O)(OR 11 ) 2 ; each R 11 is independently for each occurrence R a or a monovalent cationic group; or two R 11 , together with the atoms to which they are attached, form a 4-8 membered cyclic phosphate group, or two R 11 together represent a divalent cationic group

R 5 is halo, —CN, optionally substituted C 1-6 alkyl, alkynyl, hydroxy, optionally substituted C 1-6 alkoxy, nitro, —N(R a ) 2 , —C(O)N(R a ) 2 , —CO 2 R a or —C(O)R a

each R a independently is C 1-6 alkyl;

each R b independently is, for each occurrence, ═O, —OR a , haloC 1-3 alkyloxy, —SR a , —N(R c ) 2 , halo, —CF 3 , —CN, —S(O) 2 N(R c ) 2 , —S(O) 2 R a , —C(O)R a , —CO 2 R a , —C(O)N(R c ) 2 , —N(R a )—S(O) 2 H, or —C(R a ) 2 —N(R c ) 2 ; and

Z 1 is CH, CR 2 , C-halo or C-optionally substituted C 1-6 alkyl, or N.

7. The compound of claim 1 , or a salt thereof, having a formula IIb

wherein:

each R 1 independently is, for each occurrence, H, optionally substituted C 1-6 alkyl, C(O)—C 1-6 alkyl, CO 2 —C 1-6 alkyl or R 50 ;

each R 50 is —C(R 9 ) 2 -A-R 10 , where A is O or S; each R 9 is independently for each occurrence H, optionally substituted C 1-6 alkyl, optionally substituted C 6-10 aryl or optionally substituted C 7-16 arylalkyl; or alternatively, two R 9 , together with the carbon to which they are attached, form an optionally substituted C 3-8 cycloalkyl group or an optionally substituted 3-8 membered heteroalicyclyl; R 10 is R a or —P(O)(OR 11 ) 2 ; each R 11 is independently for each occurrence R a or a monovalent cationic group; or two R 11 , together with the atoms to which they are attached, form a 4-8 membered cyclic phosphate group, or two R 11 together represent a divalent cationic group

R 5 is halo, —CN, optionally substituted C 1-6 alkyl, alkynyl, hydroxy, optionally substituted C 1-6 alkoxy, nitro, —N(R a ) 2 , —C(O)N(R a ) 2 , —CO 2 R a or —C(O)R a

each R a independently is C 1-6 alkyl;

each R b independently is, for each occurrence, ═O, —OR a , haloC 1-3 alkyloxy, —SR a , —N(R c ) 2 , halo, —CF 3 , —CN, —S(O) 2 N(R c ) 2 , —S(O) 2 R a , —C(O)R a , —CO 2 R a , —C(O)N(R c ) 2 , —N(R a )—S(O) 2 H, or —C(R a ) 2 —N(R c ) 2 ; and

Z 1 is CH, CR 2 , C-halo or C-optionally substituted C 1-6 alkyl, or N.

8. The compound of claim 1 , or a salt thereof, having a formula IIc

wherein:

each R 1 independently is, for each occurrence, H, optionally substituted C 1-6 alkyl, C(O)—C 1-6 alkyl, CO 2 —C 1-6 alkyl or R 50 ;

each R 50 is —C(R 9 ) 2 -A-R 10 , where A is O or S; each R 9 is independently for each occurrence H, optionally substituted C 1-6 alkyl, optionally substituted C 6-10 aryl or optionally substituted C 7-16 arylalkyl; or alternatively, two R 9 , together with the carbon to which they are attached, form an optionally substituted C 3-8 cycloalkyl group or an optionally substituted 3-8 membered heteroalicyclyl; R 10 is R a or —P(O)(OR 11 ) 2 ; each R 11 is independently for each occurrence R a or a monovalent cationic group; or two R 11 , together with the atoms to which they are attached, form a 4-8 membered cyclic phosphate group, or two R 11 together represent a divalent cationic group

R 5 is halo, —CN, optionally substituted C 1-6 alkyl, alkynyl, hydroxy, optionally substituted C 1-6 alkoxy, nitro, —N(R a ) 2 , —C(O)N(R a ) 2 , —CO 2 R a or —C(O)R a

each R a independently is C 1-6 alkyl;

each R b is independently is, for each occurrence, ═O, —OR a , haloC 1-3 alkyloxy, —SR a , —N(R c ) 2 , halo, —CF 3 , —CN, —S(O) 2 N(R c ) 2 , —S(O) 2 R a , —C(O)R a , —CO 2 R a , —C(O)N(R c ) 2 , —N(R a )—S(O) 2 H, or —C(R a ) 2 —N(R c ) 2 ; and

Z 1 is CH, CR 2 , C-halo or C-optionally substituted C 1-6 alkyl, or N.

9. The compound of claim 1 , or a salt thereof, having a formula IId

wherein:

each R 1 independently is, for each occurrence, H, optionally substituted C 1-6 alkyl, C(O)—C 1-6 alkyl, CO 2 —C 1-6 alkyl or R 50 ;

each R 50 is —C(R 9 ) 2 -A-R 10 , where A is O or S; each R 9 is independently for each occurrence H, optionally substituted C 1-6 alkyl, optionally substituted C 6-10 aryl or optionally substituted C 7-16 arylalkyl; or alternatively, two R 9 , together with the carbon to which they are attached, form an optionally substituted C 3-8 cycloalkyl group or an optionally substituted 3-8 membered heteroalicyclyl; R 10 is R a or —P(O)(OR 11 ) 2 ; each R 11 is independently for each occurrence R a or a monovalent cationic group; or two R 11 , together with the atoms to which they are attached, form a 4-8 membered cyclic phosphate group, or two R 11 together represent a divalent cationic group

R 5 is halo, —CN, optionally substituted C 1-6 alkyl, alkynyl, hydroxy, optionally substituted C 1-6 alkoxy, nitro, —N(R a ) 2 , —C(O)N(R a ) 2 , —CO 2 R a or —C(O)R a

each R a independently is C 1-6 alkyl;

each R b independently is, for each occurrence, ═O, —OR a , haloC 1-3 alkyloxy, —SR a , —N(R c ) 2 , halo, —CF 3 , —CN, —S(O) 2 N(R c ) 2 , —S(O) 2 R a , —C(O)R a , —CO 2 R a , —C(O)N(R c ) 2 , —N(R a )—S(O) 2 H, or —C(R a ) 2 —N(R c ) 2 ; and

Z 1 is CH, CR 2 , C-halo or C-optionally substituted C 1-6 alkyl, or N.

10. The compound of claim 1 , or a salt thereof, having a formula IIe

wherein:

each R 1 independently is, for each occurrence, H, optionally substituted C 1-6 alkyl, C(O)—C 1-6 alkyl, CO 2 —C 1-6 alkyl or R 50 ;

each R 50 is —C(R 9 ) 2 -A-R 10 , where A is O or S; each R 9 is independently for each occurrence H, optionally substituted C 1-6 alkyl, optionally substituted C 6-10 aryl or optionally substituted C 7-16 arylalkyl; or alternatively, two R 9 , together with the carbon to which they are attached, form an optionally substituted C 3-8 cycloalkyl group or an optionally substituted 3-8 membered heteroalicyclyl; R 10 is R a or —P(O)(OR 11 ) 2 ; each R 11 is independently for each occurrence R a or a monovalent cationic group; or two R 11 , together with the atoms to which they are attached, form a 4-8 membered cyclic phosphate group, or two R 11 together represent a divalent cationic group

R 5 is halo, —CN, optionally substituted C 1-6 alkyl, alkynyl, hydroxy, optionally substituted C 1-6 alkoxy, nitro, —N(R a ) 2 , —C(O)N(R a ) 2 , —CO 2 R a or —C(O)R a

each R a independently is C 1-6 alkyl;

each R b independently is, for each occurrence, ═O, —OR a , haloC 1-3 alkyloxy, —SR a , —N(R c ) 2 , halo, —CF 3 , —CN, —S(O) 2 N(R c ) 2 , —S(O) 2 R a , —C(O)R a , —CO 2 R a , —C(O)N(R c ) 2 , —N(R a )—S(O) 2 H, or —C(R a ) 2 —N(R c ) 2 ; and

Z 1 is CH, CR 2 , C-halo or C-optionally substituted C 1-6 alkyl, or N.

11. A pharmaceutical composition, comprising a compound, or a salt thereof, having a formula I

wherein:

X and Y each independently is O, S, S(O), SO 2 or NR 1 ;

each R 1 independently is, for each occurrence, H, optionally substituted C 1-6 alkyl, C(O)—C 1-6 alkyl, CO 2 —C 1-6 alkyl or R 50 ;

each R 50 is —C(R 9 ) 2 -A-R 10 , where A is O or S; each R 9 is independently for each occurrence H, optionally substituted C 1-6 alkyl, optionally substituted C 6-10 aryl or optionally substituted C 7-16 arylalkyl; or alternatively, two R 9 , together with the carbon to which they are attached, form an optionally substituted C 3-8 cycloalkyl group or an optionally substituted 3-8 membered heteroalicyclyl; R 10 is R a or —P(O)(OR 11 ) 2 ; each R 11 is independently for each occurrence R a or a monovalent cationic group; or two R 11 , together with the atoms to which they are attached, form a 4-8 membered cyclic phosphate group, or two R 11 together represent a divalent cationic group;

ring A is bicyclic;

each R 2 independently is, for each occurrence, H, R e , R b , R e substituted with one or more of the same or different R a and/or R b , —OR e substituted with one or more of the same or different R a and/or R b , —SR e substituted with one or more of the same or different R a and/or R b , —C(O)R e substituted with one or more of the same or different R a and/or R b , —N(R a )R e where R e is substituted with one or more of the same or different R a and/or R b , —S(O) 2 R e substituted with one or more of the same or different R a and/or R b , —N(R a )—S(O) 2 R e where R e is substituted with one or more of the same or different R a and/or R b , —B(OR a ) 2 , —B(N(R c ) 2 ) 2 , —(C(R a ) 2 ) m —R b , —O—(C(R a ) 2 ) m —R b , —S—(C(R a ) 2 ) m —R b , —O—(C(R b ) 2 ) m —R a , —N(R a )—(C(R a ) 2 ) m —R b , —O—(CH 2 ) m —CH((CH 2 ) m R b )R b , —C(O)N(R a )—(C(R a ) 2 ) m —R b , —O—(C(R a ) 2 ) m —C(O)N(R a )—(C(R a ) 2 ) m —R b , —N((C(R a ) 2 ) m R b ) 2 , —S—(C(R a ) 2 ) m —C(O)N(R a )—(C(R a ) 2 ) m —R b , —N(R a )—C(O)—N(R a )—(C(R a ) 2 ) m —R b , —N(R a )—C(O)—(C(R a ) 2 ) m —C(R a )(R b ) 2 or —N(R a )—(C(R a ) 2 ) m —C(O)—N(R a )—(C(R a ) 2 ) m —R b ;

each R a independently is, for each occurrence, H, deuterium, C 1-6 alkyl, C 3-8 cycloalkyl, C 4-11 cycloalkylalkyl, C 6-10 aryl, C 7-16 arylalkyl, 2-6 membered heteroalkyl, 3-10 membered heteroalicyclyl, 4-11 membered heteroalicyclylalkyl, 5-15 membered heteroaryl or 6-16 membered heteroarylalkyl;

each R b independently is, for each occurrence, ═O, —OR a , —O—(C(R a ) 2 ) m —OR a , haloC 1-3 alkyloxy, ═S, —SR a , ═NR a , ═NOR a , —N(R c ) 2 , halo, —CF 3 , —CN, —NC, —OCN, —SCN, —NO, —NO 2 , ═N 2 , —N 3 , —S(O)R a , —S(O) 2 R a , —SO 3 R a , —S(O)N(R c ) 2 , —S(O) 2 N(R c ) 2 , —OS(O)R a , —OS(O) 2 R a , —OSO 3 R a , —OS(O) 2 N(R c ) 2 , —C(O)R a , —CO 2 R a , —C(O)N(R c ) 2 , —C(NR a )—N(R c ) 2 , —C(NOH)—R a , —C(NOH)—N(R c ) 2 , —OC(O)R a , —OC(O)OR a , —OC(O)N(R c ) 2 , —OC(NH)—N(R c ) 2 , —OC(NR a )—N(R c ) 2 , —N(R a )—S(O) 2 H, —[N(R a )C(O)] n R a , —[N(R a )C(O)] n OR a , —[N(R a )C(O)] n N(R c ) 2 or —[N(R a )C(NR a )] n —N(R c ) 2 ;

each R c independently is, for each occurrence, R a , or, alternatively, two R c are taken together with the nitrogen atom to which they are bonded to form a 3 to 10-membered heteroalicyclyl or a 5-10 membered heteroaryl which may optionally include one or more of the same or different additional heteroatoms and which is optionally substituted with one or more of the same or different R a and/or R d groups;

each R d is ═O, —OR a , haloC 1-3 alkyloxy, C 1-6 alkyl, ═S, —SR a , ═NR a , ═NOR a , —N(R a ) 2 , halo, —CF 3 , —CN, —NC, —OCN, —SCN, —NO, —NO 2 , ═N 2 , —N 3 , —S(O)R a , —S(O 2 )R a , —SO 3 R a , —S(O)N(R a ) 2 , —S(O) 2 N(R a ) 2 , —OS(O)R a , —OS(O) 2 R a , —OSO 3 R a , —OS(O) 2 N(R a ) 2 , —C(O)R a , —CO 2 R a , —C(O)N(R a ) 2 , —C(NR a )N(R a ) 2 , —C(NOH)R a , —C(NOH)N(R a ) 2 , —OCO 2 R a , —OC(O)N(R a ) 2 , —OC(NR a )N(R a ) 2 , —[N(R a )C(O)] n R a , —(C(R a ) 2 ) n —OR a , —N(R a )—S(O) 2 R a , —C(O)—C 1-6 haloalkyl, —S(O) 2 C 1-6 haloalkyl, —OC(O)R a , —O(C(R a ) 2 ) m —OR a , —S(C(R a ) 2 ) m —OR a , —N(R a )C 1-6 haloalkyl, —P(O)(OR a ) 2 , —N(R a )—(C(R a ) 2 ) m —OR a , —[N(R a )C(O)] n OR a , —[N(R a )C(O)] n N(R a ) 2 , —[N(R a )C(NR a )] n N(R a ) 2 or —N(R a )C(O)C 1-6 haloalkyl; or two R d , taken together with the atom or atoms to which they are attached, combine to form a 3-10 membered partially or fully saturated mono or bicyclic ring, optionally containing one or more heteroatoms and optionally substituted with one or more R a ;

each R e independently is, for each occurrence, C 1-6 alkyl, C 3-8 cycloalkyl, C 4-11 cycloalkylalkyl, C 6-10 aryl, C 7-16 arylalkyl, 2-6 membered heteroalkyl, 3-10 membered heteroalicyclyl, 4-11 membered heteroalicyclylalkyl, 5-15 membered heteroaryl or 6-16 membered heteroarylalkyl;

p is 0, 1, 2, 3 or 4;

each m is 1, 2 or 3;

each n is 0, 1, 2 or 3;

two R 2 groups, taken together with the atom or atoms to which they are attached, combine to form a 4-10 membered partially or fully saturated mono or bicyclic ring, optionally containing one or more heteroatoms and optionally substituted with one or more R a and/or R b ;

Z 1 and Z 2 are each independently CH, CR 2 or N;

R 3 is H, optionally substituted C 1-6 alkyl or R 50 ;

R 4 is H, optionally substituted C 1-6 alkyl or R 50 ; and

R 5 is halo, —CN, optionally substituted C 1-6 alkyl, alkynyl, hydroxy, optionally substituted C 1-6 alkoxy, nitro, —N(R a ) 2 , —C(O)N(R a ) 2 , —CO 2 R a or —C(O)R a .

12. The pharmaceutical composition of claim 11 wherein the compound, or a salt thereof, has a formula IA3

wherein R b is OH, C 1-6 alkyl, —CO 2 C 1-6 alkyl, —C(O)C 1-6 alkyl or —S(O) 2 C 1-6 alkyl.

13. The pharmaceutical composition of claim 11 wherein the compound, or a salt thereof, has a

wherein:

each R 1 independently is, for each occurrence, H, optionally substituted C 1-6 alkyl, C(O)—C 1-6 alkyl, CO 2 —C 1-6 alkyl or R 50 ;

each R 50 is —C(R 9 ) 2 -A-R 10 , where A is O or S; each R 9 is independently for each occurrence H, optionally substituted C 1-6 alkyl, optionally substituted C 6-10 aryl or optionally substituted C 7-16 arylalkyl; or alternatively, two R 9 , together with the carbon to which they are attached, form an optionally substituted C 3-8 cycloalkyl group or an optionally substituted 3-8 membered heteroalicyclyl; R 10 is R a or —P(O)(OR 11 ) 2 ; each R 11 is independently for each occurrence R a or a monovalent cationic group; or two R 11 , together with the atoms to which they are attached, form a 4-8 membered cyclic phosphate group, or two R 11 together represent a divalent cationic group

R 5 is halo, —CN, optionally substituted C 1-6 alkyl, alkynyl, hydroxy, optionally substituted C 1-6 alkoxy, nitro, —N(R a ) 2 , —C(O)N(R a ) 2 , —CO 2 R a or —C(O)R a

each R a independently is C 1-6 alkyl;

each R b independently is, for each occurrence, ═O, —OR a , haloC 1-3 alkyloxy, —SR a , —N(R c ) 2 , halo, —CF 3 , —CN, —S(O) 2 N(R c ) 2 , —S(O) 2 R a , —C(O)R a , —CO 2 R a , —C(O)N(R c ) 2 , —N(R a )—S(O) 2 H, or —C(R a ) 2 —N(R c ) 2 ; and

Z 1 is CH, CR 2 , C-halo or C-optionally substituted C 1-6 alkyl, or N.

14. The composition according to claim 11 further comprising an excipient, a second therapeutic, or combinations thereof.

Assignments (4)
SECURITY INTEREST Recorded May 8, 2026
From: RIGEL PHARMACEUTICALS, INC.
To: MIDCAP FUNDING IV TRUST
Reel/Frame 075576/0880 →
SECURITY INTEREST Recorded Aug 25, 2022
From: RIGEL PHARMACEUTICALS, INC.
To: MIDCAP FINANCIAL TRUST
Reel/Frame 061327/0712 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 18, 2017
From: LI, HUI; HECKRODT, THILO J.; CHEN, YAN; MCMURTRIE, DARREN JOHN; TAYLOR, VANESSA; SINGH, RAJINDER; DING, PINGYU; THOTA, SAMBAIAH; YEN, ROSE
To: RIGEL PHARMACEUTICALS, INC.
Reel/Frame 042046/0990 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 18, 2017
From: LI, HUI; HECKRODT, THILO J.; CHEN, YAN; MCMURTRIE, DARREN JOHN; TAYLOR, VANESSA; SINGH, RAJINDER; DING, PINGYU; THOTA, SAMBAIAH; YEN, ROSE
To: RIGEL PHARMACEUTICALS, INC.
Reel/Frame 042047/0015 →
Continuity (8)
Continuation 14793506 · Jul 7, 2015
Continuation 14250329 · Apr 10, 2014
Continuation 14023158 · Sep 10, 2013
Continuation 13283471 · Oct 27, 2011
Continuation 12692493 · Jan 22, 2010
Provisional Application 61241630 · Sep 11, 2009
Provisional Application 61147059 · Jan 23, 2009
Related Publication 20170137411A1 · May 18, 2017