US2023110077A1PendingUtilityA1

1,2,4-Oxadiazole and Thiadiazole Compounds as Immunomodulators

Assignee: AURIGENE DISCOVERY TECH LTDPriority: Mar 10, 2015Filed: Oct 10, 2022Published: Apr 13, 2023
Est. expiryMar 10, 2035(~8.6 yrs left)· nominal 20-yr term from priority
C07D 271/10C07K 5/06078A61K 45/06C07K 5/0812C07D 413/04A61P 35/02A61P 31/04C07D 413/06A61P 31/10C07D 413/12A61P 43/00A61K 38/05A61P 37/02A61P 35/00A61K 31/4245C07D 271/06A61P 31/12
78
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Claims

Abstract

The present invention relates to 1,2,4-oxadiazole and thiadiazole compounds of formula (I) and their use to inhibit the programmed cell death 1 (PD1) signaling pathway and/or for treatment of disorders by inhibiting an immunosuppressive signal induced by PD-1, PD-L1 or PD-L2.

Claims

exact text as granted — not AI-modified
We claim: 
     
         1 . A compound of formula (I): 
       
         
           
           
               
               
           
         
       
       or a pharmaceutically acceptable salt thereof; wherein,
 X is O or S; 
 R 1  and R 2  are each independently a side chain of an amino acid, hydrogen, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl or cycloalkyl; wherein each (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl or cycloalkyl is optionally substituted by one or more substituents, selected from amino, alkylamino, acylamino, carboxylic acid, carboxylate, carboxylic acid ester, thiocarboxylate, thioacid, —CONR 7 R 8 , hydroxy, cycloalkyl, (cycloalkyl)alkyl, aryl, arylalkyl, heterocyclyl, (heterocyclyl)alkyl, heteroaryl, (heteroaryl)alkyl, guanidino, —SH and —S(alkyl); optionally wherein cycloalkyl, aryl, heterocyclyl or heteroaryl is further substituted by one or more substituents and optionally wherein two or three carbon atoms of the (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl or (C 2 -C 6 )alkynyl form part of a 3-7-membered carbocyclic or heterocyclic ring; 
 R 3  is —S(O) p -[Aaa1] m ; 
 R 6  is hydrogen, alkyl, aminoalkyl, hydroxyalkyl, alkoxyalkyl, or acyl; 
 R 7  and R 8  independently are hydrogen, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, aryl or heterocyclyl; wherein each (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, aryl or heterocyclyl is optionally substituted by one or more substituents selected from halogen, hydroxyl, amino, nitro, cyano, cycloalkyl, heterocyclyl, heteroaryl, aryl, guanidino, (cycloalkyl)alkyl, (heterocyclyl)alkyl and (heteroaryl)alkyl; optionally wherein two or three carbon atoms of the (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl or (C 2 -C 6 )alkynyl form part of a 3-7-membered carbocyclic or heterocyclic ring; or 
 
       alternatively R 7  and R 8  together with the nitrogen to which they are attached form an optionally substituted 3-7-membered ring containing 0-2 additional heteroatoms independently selected from N, O and S in any stable combination; wherein the optional substituent at each occurrence is selected from hydroxyl, —COOH, —COO-alkyl, amide, halo, amino, nitro and cyano; 
       [Aaa1] represent an amino acid residue having a side chain; wherein a C-terminal carboxyl moiety of the amino acid residue is a free C-terminal carboxyl moiety or an alkyl substituted C-terminal carboxyl moiety or the C-terminal moiety is optionally substituted amido, or optionally substituted heteroaryl, and an N-terminal amino moiety of the amino acid residue is a free N-terminus;
 R a  is hydrogen or alkyl; 
 R b  is hydrogen, alkyl, aminoalkyl, hydroxyalkyl or alkoxyalkyl; or R b  and R 2 , together with the atoms to which they are attached, form pyrrolidine or piperidine, each optionally substituted with one or more substituents independently selected from hydroxyl, halo, amino, cyano and alkyl; 
 m is 1, 2, or 3; and 
 p is 1 or 2. 
 
     
     
         2 . The compound of  claim 1 , wherein the compound is of formula (IA): 
       
         
           
           
               
               
           
         
       
       or a pharmaceutically acceptable salt thereof. 
     
     
         3 . The compound of  claim 1 , wherein R b  is H. 
     
     
         4 . The compound of  claim 1 , wherein the side chain of [Aaa1] comprises a (C 1 -C 4 )alkyl optionally substituted by one or more substituents, selected from amino, alkylamino, acylamino, carboxylic acid, carboxylate, thiocarboxylate, thioacid, —CONR 7 R 8 , hydroxy, cycloalkyl, (cycloalkyl)alkyl, aryl, heterocyclyl, heteroaryl, guanidino, —SH, and —S(alkyl); optionally wherein cycloalkyl, aryl, heterocyclyl or heteroaryl. 
     
     
         5 . The compound of  claim 1 , wherein the side chain of [Aaa1] comprises a (C 1 -C 4 )alkyl substituted by one or more substituents, selected from amino, acylamino, carboxylic acid, —CONR 7 R 8 , hydroxy, cycloalkyl, aryl, heteroaryl, guanidino, —SH and —S(alkyl); and wherein R 7  and R 8  independently are hydrogen, alkyl, aryl or heterocyclyl. 
     
     
         6 . The compound of  claim 1 , wherein R a  is H. 
     
     
         7 . The compound of  claim 1 , wherein R 1  is (C 1 -C 8 )alkyl optionally substituted by one or more substituents, selected from amino, alkylamino, acylamino, carboxylic acid, carboxylate, carboxylic acid ester, thiocarboxylate, thioacid, —CONR 7 R 8 , hydroxy, cycloalkyl, (cycloalkyl)alkyl, aryl, arylalkyl, heterocyclyl, (heterocyclyl)alkyl, heteroaryl, (heteroaryl)alkyl, guanidino, —SH, and —S(alkyl); and optionally wherein cycloalkyl, aryl, heterocyclyl or heteroaryl. 
     
     
         8 . The compound of  claim 1 , wherein R 1  is (C 1 -C 8 )alkyl substituted by one or more substituents selected from amino, acylamino, carboxylic acid, —CONR 7 R 8 , hydroxy, cycloalkyl, aryl, heteroaryl, guanidino, —SH, and —S(alkyl); and wherein R 7  and R 8  independently are hydrogen, alkyl or aryl. 
     
     
         9 . The compound of  claim 1 , wherein R 1  is the side chain of an amino acid. 
     
     
         10 . The compound of  claim 1 , wherein R 1  is a side chain of an amino acid selected from Ala, Asn, Asp, Tyr, Lys, Ser, Thr, Gln, Ile, Val, Glu, Arg, Leu, Trp, His, Met, Cys, and Phe. 
     
     
         11 . The compound of  claim 1 , wherein R 2  is (C 1 -C 8 )alkyl optionally substituted by one or more substituents, selected from amino, alkylamino, acylamino, carboxylic acid, carboxylate, carboxylic acid ester, thiocarboxylate, thioacid, —CONR 7 R 8 , hydroxy, cycloalkyl, (cycloalkyl)alkyl, aryl, arylalkyl, heterocyclyl, (heterocyclyl)alkyl, heteroaryl, (heteroaryl)alkyl, guanidino, —SH, and —S(alkyl); and optionally wherein cycloalkyl, aryl, heterocyclyl or heteroaryl. 
     
     
         12 . The compound of  claim 1 , wherein R 2  is (C 1 -C 8 )alkyl substituted by one or more substituents, selected from amino, acylamino, carboxylic acid, —CONR 7 R 8 , hydroxy, cycloalkyl, aryl, heteroaryl, guanidino, —SH and —S(alkyl); and wherein R 7  and R 8  independently are hydrogen or alkyl. 
     
     
         13 . The compound of  claim 1 , wherein R 2  is the side chain of an amino acid. 
     
     
         14 . The compound of  claim 1 , wherein R 2  is a side chain of an amino acid selected from Ala, Asn, Ile, Lys, Phe, Glu, Asp, Trp, Val, Ser, Gln, Tyr, Thr, Met, Arg, and Leu. 
     
     
         15 . The compound of  claim 1 , wherein R b  and R 2 , together with the atoms to which they are attached, form pyrrolidine or piperidine, optionally substituted with one or more substituents, independently selected from hydroxyl, halo, amino, cyano and alkyl. 
     
     
         16 . The compound of  claim 1 , wherein R 6  is H. 
     
     
         17 . The compound of  claim 1 , wherein at least one of the amino acid residues is a D amino acid residue. 
     
     
         18 . The compound of  claim 1 , wherein at least one of the amino acid residues is an L amino acid residue. 
     
     
         19 . The compound of  claim 1 , wherein the compound is: 
       
         
           
                 
                 
               
                     
                 
                   Compound No. 
                   Structure 
                 
                     
                 
                     
                 
                 
                 
               
                   97 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   98 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   99 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   100 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   101 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   102 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   103 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   104 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   119 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   120 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   121 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   122 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   123 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
                   124 
                   
                     
                       
                       
                           
                           
                       
                     
                   
                 
                     
                 
             
                
                
                
               
               
                
               
            
             
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
       or a pharmaceutically acceptable salt thereof or a stereoisomer thereof. 
     
     
         20 . A pharmaceutical composition comprising a compound of  claim 1  and a pharmaceutically acceptable carrier.

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