US2020002345A1PendingUtilityA1

Pyrazolopyrimidine jak inhibitor compounds and methods

71
Assignee: GENENTECH INCPriority: Jul 2, 2009Filed: Sep 5, 2019Published: Jan 2, 2020
Est. expiryJul 2, 2029(~3 yrs left)· nominal 20-yr term from priority
C07D 487/04A61P 35/02A61P 17/06A61K 31/519A61P 29/00A61K 31/437C07D 403/12C07D 413/06A61K 31/445
71
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Claims

Abstract

A compound of Formula I, enantiomers, diasteriomers, tautomers or pharmaceutically acceptable salts thereof, wherein R 1 , R 2 and R 3 are defined herein, are useful as inhibitors of one or more Janus kinases. A pharmaceutical composition that includes a compound of Formula I and a pharmaceutically acceptable carrier, adjuvant or vehicle, and methods of treating or lessening the severity of a disease or condition responsive to the inhibition of a Janus kinase activity in a patient are disclosed.

Claims

exact text as granted — not AI-modified
What is claimed is: 
     
         1 . A compound of Formula I: 
       
         
           
           
               
               
           
         
         enantiomers, diastereomers or pharmaceutically acceptable salts thereof, wherein: 
         R 1  is hydrogen, C 1 -C 6  alkyl, —OR 6 , —NR 6 R 7  or halogen; 
         R 2  is 5- or 6-membered heteroaryl, wherein R 2  is optionally substituted with 1-3 R 4 ; 
         R 3  is phenyl, 5-6 membered heteroaryl, C 3 -C 6  cycloalkyl or 3-10 membered heterocyclyl, wherein R 3  is optionally substituted by 1-5 R 5 ; 
         Each R 4  is independently C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, halogen, —(C 0 -C 6  alkyl)CN, —(C 0 -C 6  alkyl)OR 6 , —(C 0 -C 6  alkyl)SR 6 , —(C 0 -C 6  alkyl)NR 6 R 7 , —(C 0 -C 6  alkyl)CF 3 , —(C 0 -C 6 alkyl)C(O)R 6 , —(C 0 -C 6  alkyl)C(O)OR 6 , —(C 0 -C 6 alkyl)C(O)NR 6 R 7 , —(C 0 -C 6  alkyl)NR 6 C(O)R 7 , —(C 0 -C 6  alkyl)C(O)3-6 membered heterocyclyl, —(C 0 -C 6  alkyl)(C 3 -C 6  cycloalkyl), —(C 0 -C 6  alkyl)phenyl, —(C 0 -C 6  alkyl)5-6 membered heteroaryl or —(C 0 -C 6  alkyl)(3-6-membered heterocyclyl), wherein R 4  is independently optionally substituted by R 15 ; 
         Each R 5  is independently C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, oxo, halogen, —(C 0 -C 3 alkyl)CN, —(C 0 -C 3  alkyl)OR 11 , —(C 0 -C 3  alkyl)SR 11 , —(C 0 -C 3 alkyl)NR 11 R 12 , —(C 0 -C 3  alkyl)OCF 3 , —(C 0 -C 3  alkyl)CF 3 , —(C 0 -C 3  alkyl)NO 2 , —(C 0 -C 3  alkyl)C(O)R 11 , —(C 0 -C 3  alkyl)C(O)OR 11 , —(C 0 -C 3  alkyl)C(O)NR 11 R 12 , —(C 0 -C 3  alkyl)NR 11 C(O)R 12 , —(C 0 -C 3  alkyl)S(O) 1-2  R 11 , —(C 0 -C 3  alkyl)NR 11 S(O) 1-2  R 12 , —(C 0 -C 3  alkyl)S(O) 1-2  NR 11 R 12 , —(C 0 -C 3  alkyl)(C 3 -C 6  cycloalkyl), —(C 0 -C 3  alkyl)(3-6-membered heterocyclyl), —(C 0 -C 3  alkyl)C(O)(3-6-membered heterocyclyl), —(C 0 -C 3  alkyl)(5-6-membered heteroaryl) or —(C 0 -C 3  alkyl)phenyl, wherein R 5  is independently optionally substituted by halogen, C 1 -C 3  alkyl, oxo, —CF 3 , —(C 0 -C 3  alkyl)OR 13  or —(C 0 -C 3  alkyl)NR 13 R 14 ; or 
         two R 5  are taken together to form —O(CH 2 ) 1-3 O—; 
         R 6  and R 7  are each independently hydrogen, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, —CN, —NR 8 R 9 , —C(O)R 8 , —C(O)OR 8 , —C(O)NR 8 R 9 , —NR 8 C(O)R 9 , —NR 8 C(O)OR 9 , —OC(O)NR 8 ,—S(O) 1-2 R 8 , —NR 8 S(O) 1-2 R 9 , —S(O) 1-2  NR 8 R 9 , C 3 -C 6  cycloalkyl, phenyl, 3-6 membered heterocyclyl or 5-6 membered heteroaryl, wherein said R 6  and R 7  are independently optionally substituted by R 20 , or 
         R 6  and R 7  are taken together with the atom to which they are attached to form a 3-6-membered heterocyclyl, optionally substituted by halogen, oxo, —CF 3  or C 1 -C 3  alkyl; 
         R 8  and R 9  are each independently hydrogen or C 1 -C 3  alkyl; or 
         R 8  and R 9  are taken together with the atom to which they are attached to form a 3-6-membered heterocyclyl, optionally substituted by halogen, oxo, —CF 3  or C 1 -C 3  alkyl; 
         R 11  is independently hydrogen, C 1 -C 6  alkyl, C 3 -C 6  cycloalkyl, 3-6 membered heterocyclyl, —C(O)R 13 , —C(O)OR 13 , —C(O)NR 13 R 14 , —NR 13 C(O)R 14 , —S(O) 1-2  R 13 , —NR 13 S(O) 1-2 R 14  or —S(O) 1-2  NR 13 R 14 , wherein said alkyl, cycloalkyl and heterocyclyl are independently optionally substituted by oxo, C 1 -C 3  alkyl, OR 13 , NR 13 R 14  or halogen; 
         Each R 12  is independently hydrogen or C 1 -C 3  alkyl, wherein said alkyl is independently optionally substituted by halogen or oxo; or 
         R 11  and R 12  are taken together with the atom to which they are attached to form a 3-6-membered heterocyclyl, optionally substituted by halogen, oxo, —CF 3  or C 1 -C 3  alkyl; 
         R 13  and R 14  are each independently hydrogen or C 1 -C 3  alkyl optionally substituted by halogen or oxo; or 
         R 13  and R 14  are taken together with the atom to which they are attached to form a 3-6-membered heterocyclyl, optionally substituted by halogen, oxo, —CF 3  or C 1 -C 3  alkyl; 
         R 15  is C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, oxo, halogen, —CN, —OR 16 , —SR 16 , —NR 16 R 17 , —OCF 3 , —CF 3 , —C(O)R 16 , —C(O)OR 16 , —C(O)NR 16 R 17 , —NR 16 C(O)R 17 , —NR 16 C(O)OR 17 , —OC(O)NR 16 , C 3 -C 6  cycloalkyl, 3-6-membered heterocyclyl, —C(O)(3-6-membered heterocyclyl, 5-6-membered heteroaryl or phenyl, wherein R 15  is independently optionally substituted by halogen, C 1 -C 3  alkyl, oxo, —CN, —CF 3 , —NR 18 R 19 ; 
         R 16  and R 17  are independently hydrogen or C 1 -C 6  alkyl optionally substituted by oxo or halogen; or 
         R 16  and R 17  are taken together with the atom to which they are attached to form a 3-6 membered heterocyclyl optionally substituted by oxo, halogen or C 1 -C 3  alkyl; 
         R 18  and R 19  are independently hydrogen or C 1 -C 6  alkyl optionally substituted by oxo or halogen; or 
         R 18  and R 19  are taken together with the atom to which they are attached to form a 3-6 membered heterocyclyl optionally substituted by oxo, halogen or C 1 -C 3  alkyl; 
         R 20  is C 1 -C 6  alkyl, oxo, halogen, —OR 21 , —NR 21 R 22 , —CN, C 3 -C 6  cycloalkyl, phenyl, 3-6 membered heterocyclyl or 5-6 membered heteroaryl, wherein R 20  is optionally substituted by oxo, halogen or C 1 -C 3  alkyl; and 
         R 20  and R 21  are independently hydrogen or C 1 -C 6  alkyl optionally substituted by oxo or halogen; or 
         R 20  and R 21  are taken together with the atom to which they are attached to form a 3-6 membered heterocyclyl optionally substituted by oxo, halogen or C 1 -C 3  alkyl. 
         with the proviso that said compound is other than N-(5-methyl-4-(4-propylphenyl)thiazol-2-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide; N-(4-(4-chlorophenyl)thiazol-2-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide; or N-(3-methyl-1-phenyl-1H-pyrazol-5-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide. 
       
     
     
         2 . The compound of  claim 1 , wherein R 1  is hydrogen or —NH 2 . 
     
     
         3 . The compound of  claim 1 , wherein R 2  is selected from pyrazolyl or thiazolyl optionally substituted with 1-3 R 4 . 
     
     
         4 . The compound of  claim 1 , wherein R 2  is: 
       
         
           
           
               
               
           
         
       
       wherein
 R 10  is hydrogen or R 4 . 
 
     
     
         5 . The compound of  claim 1 , wherein R 4  is independently —(C 0 -C 6  alkyl)OR 6 , —(C 0 -C 6  alkyl)SR 6 , halogen, —(C 0 -C 6  alkyl)CN, C 1 -C 6  alkyl, C 2 -C 6  alkenyl or C 2 -C 6  alkynyl, —(C 0 -C 6  alkyl)C(O)OR 6 , —(C 0 -C 6  alkyl)C(O)NR 6 NR 7 , —(C 0 -C 6  alkyl)OC(O)NR 6 , —(C 0 -C 6  alkyl)NR 6 C(O)OR 7 , —(C 0 -C 6  alkyl)NR 6 C(O)NR 7  or —(C 0 -C 6  alkyl)NR 6 C(O)R 7 , —(C 0 -C 6  alkyl)(C 3 -C 6  cycloalkyl), —(C 0 -C 6  alkyl)C(O)(3-6-membered heterocyclyl), —(C 0 -C 6  alkyl)(3-6-membered heterocyclyl), —(C 0 -C 6  alkyl)NR 6 R 7  or —(C 0 -C 6  alkyl)CF 3 , wherein R 4  is independently optionally substituted by R 15 . 
     
     
         6 . The compound of  claim 5 , wherein R 4  is independently selected from: F, Cl, Br, I, —CH 2 CN, —CH 2 CH 2 CN, —CH(CH 3 )CN, 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein the wavy line represents the point of attachment to R 2    
     
     
         7 . The compound of  claim 1 , wherein R 3  is phenyl, pyridinyl or 4-6 membered heterocyclyl, wherein R 3  is optionally substituted by R 5 . 
     
     
         8 . The compound of  claim 1 , wherein R 5  is independently C 1 -C 6  alkyl, halogen, oxo, —CN, —(C 0 -C 3  alkyl)OR 11 , —(C 0 -C 3  alkyl)SR 11 , —(C 0 -C 3  alkyl)NR 11 R 12 , —(C 0 -C 3  alkyl)OCF 3  or —CF 3 , wherein said alkyl is independently optionally substituted by halogen, C 1 -C 3  alkyl, oxo, —CF 3 , —(C 0 -C 3  alkyl)OR 13  or —(C 0 -C 3  alkyl)NR 13 R 14 . 
     
     
         9 . The compound of  claim 7 , wherein R 3  is selected from: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein the wavy line represents the point of attachment to R 2 . 
     
     
         10 . The compound of  claim 1 , wherein R 3  is phenyl optionally substituted by 1-2 R 5 . 
     
     
         11 . The compound of  claim 1 , wherein —R 2 -R 3  is: 
       
         
           
           
               
               
           
         
       
       wherein
 n is 0,1,2 or 3. 
 
     
     
         12 . A compound of  claim 1 , enantiomers, diastereomers or pharmaceutically acceptable salts thereof, wherein:
 R 1  is hydrogen, C 1 -C 6  alkyl, —OR 6 , —NR 6 R 7  or halogen;   R 2  is 5- or 6-membered heteroaryl, wherein R 2  is optionally substituted with 1-3 R 4 ;   R 3  is phenyl, 5- or 6-membered heteroaryl, wherein R 3  is optionally substituted by 1-5 R 5 ;   R 4  is independently C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, halogen, —(C 0 -C 6  alkyl)OR 6 , —(C 0 -C 6  alkyl)SR 6 , —(C 0 -C 6  alkyl)NR 6 R 7 , —(C 0 -C 6  alkyl)CF 3 , —(C 0 -C 6  alkyl)C(O)R 6 , —(C 0 -C 6  alkyl)C(O)OR 6 , —(C 0 -C 6  alkyl)C(O)NR 6 R 7 , —(C 0 -C 6  alkyl)(C 3 -C 6  cycloalkyl) or —(C 0 -C 6  alkyl)(3-6-membered heterocyclyl), wherein R 4  is independently optionally substituted by C 1 -C 3  alkyl, oxo, halogen, —CF 3 , —OR 8  or —NR 8 R 9 ;   R 5  is independently C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, halogen, —(C 0 -C 3  alkyl)CN, —(C 0 -C 3 alkyl)OR 11 , —(C 0 -C 3  alkyl)SR 11 , —(C 0 -C 3  alkyl)NR 11 R 12 , —(C 0 -C 3  alkyl)OCF 3 , —(C 0 -C 3  alkyl)CF 3 , —(C 0 -C 3  alkyl)NO 2 , —(C 0 -C 3  alkyl)C(O)R 11 , —(C 0 -C 3  alkyl)C(O)OR 11 , —(C 0 -C 3  alkyl)C(O)NR 11 R 12 , —(C 0 -C 3  alkyl)NR 11 C(O)R 12 , —(C 0 -C 3  alkyl)S(O) 1-2  R 11 , —(C 0 -C 3  alkyl)NR 11 S(O) 1-2  R 12 , —(C 0 -C 3  alkyl)S(O) 1-2  NR 11 R 12 , —(C 0 -C 3  alkyl)(C 3 -C 6  cycloalkyl), —(C 0 -C 3  alkyl)(3-6-membered heterocyclyl), —(C 0 -C 3  alkyl)C(O)(3-6-membered heterocyclyl), —(C 0 -C 3  alkyl)(5-6-membered heteroaryl) or —(C 0 -C 3  alkyl)phenyl, wherein R 5  is independently optionally substituted by halogen, C 1 -C 3  alkyl, oxo, —CF 3 , —(C 0 -C 3  alkyl)OR 13  or —(C 0 -C 3  alkyl)NR 13 R 14 ; or   two R 5  are taken together to form —O(CH 2 ) 1-3 O—;   R 6  is independently hydrogen, C 1 -C 3  alkyl, —C(O)R 8 , —C(O)OR 8 , —C(O)NR 8 R 9 , —NR 8 C(O)R 9 , —S(O) 1-2 R 8 , —NR 8 S(O) 1-2  R 9  or —S(O) 1-2  NR 8 R 9 , wherein said alkyl is independently optionally substituted by oxo, OH or halogen;   R 7  is independently hydrogen or C 1 -C 3  alkyl, wherein said alkyl is independently optionally substituted by halogen; or   R 6  and R 7  are taken together with the atom to which they are attached to form a 5- or 6-membered heterocyclyl, optionally substituted by halogen, oxo, —CF 3  or C 1 -C 3  alkyl;   R 8  and R 9  are independently hydrogen or C 1 -C 3  alkyl; or   R 8  and R 9  are taken together with the atom to which they are attached to form a 5- or 6-membered heterocyclyl, optionally substituted by halogen, oxo, —CF 3  or C 1 -C 3  alkyl;   R 11  is independently hydrogen, C 1 -C 3  alkyl, —C(O)R 13 , —C(O)OR 13 , —C(O)NR 13 R 14 , —NR 13 C(O)R 14 , —S(O) 1-2  R 13 , —NR 13 S(O) 1-2 R 14  or —S(O) 1-2 NR 13 R 14 , wherein said alkyl is independently optionally substituted by oxo, OH or halogen;   R 12  is independently hydrogen or C 1 -C 3  alkyl, wherein said alkyl is independently optionally substituted by halogen; or   R 11  and R 12  are taken together with the atom to which they are attached to form a 5- or 6-membered heterocyclyl, optionally substituted by halogen, oxo, —CF 3  or C 1 -C 3  alkyl; and   R 13  and R 14  are independently hydrogen or C 1 -C 3  alkyl; or   R 13  and R 14  are taken together with the atom to which they are attached to form a 5- or 6-membered heterocyclyl, optionally substituted by halogen, oxo, —CF 3  or C 1 -C 3  alkyl;   with the proviso that said compound is other than N-(5-methyl-4-(4-propylphenyl)thiazol-2-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide; N-(4-(4-chlorophenyl)thiazol-2-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide; or N-(3-methyl-1-phenyl-1H-pyrazol-5-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide.   
     
     
         13 . The compound of  claim 1 , selected from Examples 1-508. 
     
     
         14 . A pharmaceutical composition comprising a compound of  claim 1  and a pharmaceutically acceptable carrier, adjuvant or vehicle. 
     
     
         15 . A method of preventing, treating or lessening the severity of a disease or condition responsive to the inhibition of a Janus kinase activity in a patient, comprising administering to said patient a therapeutically effective amount of a compound of  claim 1 . 
     
     
         16 . The method of  claim 15 , wherein said disease or condition is cancer, polycythemia vera, essential thrombocytosis, myelofibrosis, chronic myelogenous leukemia (CML), rheumatoid arthritis, inflammatory bowel syndrome, Chron's disease, psoriasis, contact dermatitis or delayed hypersensitivity reactions. 
     
     
         17 . A kit for treating a disease or disorder responsive to the inhibition of a Janus kinase, comprising a first pharmaceutical composition comprising a compound of Formula I, and instructions for use. 
     
     
         18 . The kit of  claim 17 , further comprising a second pharmaceutical composition, which includes a chemotherapeutic agent.

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