US2017066712A1PendingUtilityA1

Novel molecules that selectively inhibit histone deacetylase 6 relative to histone deacetylase

56
Assignee: BRESLOW RONALDPriority: Oct 3, 2011Filed: Nov 18, 2016Published: Mar 9, 2017
Est. expiryOct 3, 2031(~5.2 yrs left)· nominal 20-yr term from priority
C07C 259/10C07D 209/08C07C 275/64C07C 259/06A61P 25/28C07D 215/06C07D 215/40C07D 235/06C07D 209/42C07D 209/24C07C 2602/10C07D 209/18
56
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Claims

Abstract

This invention provides a compound having the structure: wherein R 1 is H, halogen, —NR 5 R 6 , —NR 5 —C(═0)-R 6 , —NH—C(═O)—OR 7 , —OR 7 , —NO 2 , —CN, —SR 7 , —SO 2 R 7 , —CO 2 R 7 , CF 3 , —SOR 7 , —POR 7 , —C(═S)R 7 , —C(═O)—NR 5 R 6 , —CH 2 —C(═O)—NR 5 R 6 , —C(═NR 5 )R 6 , —P(═O)(OR 5 )(OR 6 ), —P(OR 5 )(OR 6 ), —C(═S)R 7 , C 1-5 alkyl, C 2-5 alkenyl, C 2-5 alkynyl, aryl, heteroaryl, or heterocyclyl, wherein R 5 , R 6 , and R 7 and are each, independently, H, C 1-5 alkyl, C 2-5 alkenyl, C 2-5 alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; m is an integer from 0 to 2; R 2 and R 3 are each, independently, H, halogen, —NH 2 , —CX 3 , —C(═O)OR 8 , C(═O)R 8 , —C(═O)NR 9 R 10 , C 1-10 alkyl, C 2-10 alkenyl, C 2-10 alkynyl, heteroalkyl, aryl, heteroaryl, or heterocyclyl; wherein X is Cl, Br, or F; R 8 , R 9 and R 10 are each, independently, H, C 1-5 alkyl, C 2-5 alkenyl, C 2-5 alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; Q is —Ar 1 —Z— or —Z—Ar 1 —Z—, wherein Ar 1 is aryl or heteroaryl; and each occurrence of Z is independently present or absent, and when present is —O—, —S—, —CH 2 —, —C(O)—, —NH—, —NH—NH—, —NHC(═O)—, —C(═O)NH—, —NHC(═O)CH 2 NH—, —NHC(═O)CH 2 C(═O)—, —N(OH)—, —CH 2 CH 2 — or —NHC(═O)CH═CH—; and R 4 is alkyl, —OR 11 or —NH—OR 11 , wherein R 11 is H, C 1-10 alkyl, C 2-10 alkenyl, C 2-10 alkynyl, aryl, heteroaryl, or heterocyclyl, and when Q is —Ar 1 —Z—, Z is absent, Ar 1 is phenyl, R 2 and R 3 are H, n=1, and R 4 is —NHOH, then R 1 is other than carbazole, tetrahydro-β-carboline, tetrahydro-γ-carboline, —C(═O)—NR 5 R 6 and —NR 5 —C(═0)-R 6 , wherein one of R 5 or R 6 is quinline and the other of R 5 or R 6 is H; or a pharmaceutically acceptable salt thereof.

Claims

exact text as granted — not AI-modified
1 - 35 . (canceled) 
     
     
         36 . A compound having the structure: 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is —NR 5 —C(═0)-R 6  or —C(═O)—NR 5 R 6 ,
 wherein 
 R 5  is 
 
       
       
         
           
           
               
               
           
         
         
           R 6  is 
         
       
       
         
           
           
               
               
           
         
         
           
             wherein 
             X is a Cl, Br, or F; and 
             R 12  is H, C 1-5  alkyl, C 2-5  alkenyl, C 2-5  alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; 
           
         
         m is an integer from 0 to 2; 
         R 2  and R 3  are each, independently, H, halogen, —NH 2 , —CX 3 , —C(═O)OR 8 , C(═O)R 8 , —C(═O) NR 9 R 10 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, heteroalkyl, aryl, heteroaryl, or heterocyclyl;
 wherein 
 X is Cl, Br, or F; 
 R 8 , R 9  and R 10  are each, independently, H, C 1-5  alkyl, C 2-5  alkenyl, C 2-5  alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; 
 
         Q is —Ar 1 —Z— or —Z—Ar 1 —Z—,
 wherein Ar 1  is 
 
       
       
         
           
           
               
               
           
         
         
           
             wherein X is a Cl, Br, or F; and 
           
           each occurrence of Z is present or absent, and when present is —O—, —S—, —CH 2 —, —C(O)—, —NH—, —NH—NH—, —NHC(═O)—, —C(═O)NH—, —NHC(═O)CH 2 NH—, —NHC(═O)CH 2 C(═O)—, —N(OH)—, —CH 2 CH 2 — or —NHC(═O)CH═CH—; and 
         
         R 4  is —NH—OR 11 ,
 wherein R 11  is H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl, 
 
       
       or a pharmaceutically acceptable salt thereof. 
     
     
         37 . The compound of  claim 36  having the structure: 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is —NR 5 —C(═0)-R 6  or —C(═O)—NR 5 R 6 ,
 wherein 
 R 5  is 
 
       
       
         
           
           
               
               
           
         
         
           R 6  is 
         
       
       
         
           
           
               
               
           
         
         
           
             wherein 
             X is a Cl, Br, or F; and 
             R 12  is H, C 1-5  alkyl, C 2-5  alkenyl, C 2-5  alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; 
           
         
         m is an integer from 0 to 2; 
         R 2  and R 3  are each, independently, H, halogen, —NH 2 , —CX 3 , —C(═O)OR 8 , C(═O)R 8 , —C(═O)NR 9 R 10 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, heteroalkyl, aryl, heteroaryl, or heterocyclyl;
 wherein 
 X is Cl, Br, or F; 
 R 8 , R 9  and R 10  are each, independently, H, C 1-5  alkyl, C 2-5  alkenyl, C 2-5  alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; 
 
         Q is —Ar 1 —Z— or —Z—Ar 1 —Z—,
 wherein Ar 1  is 
 
       
       
         
           
           
               
               
           
         
         
           
             wherein X is a Cl, Br, or F; and 
           
           each occurrence of Z is present or absent, and when present is —O—, —S—, —CH 2 —, —C(O)—, —NH—, —NH—NH—, —NHC(═O)—, —C(═O)NH—, —NHC(═O)CH 2 NH—, —NHC(═O)CH 2 C(═O)—, —N(OH)—, —CH 2 CH 2 — or —NHC(═O)CH═CH—; and 
         
         R 4  is —NH—OR 11 ,
 wherein R 11  is H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl, and 
 wherein at least one Z is present, 
 
       
       or a pharmaceutically acceptable salt thereof. 
     
     
         38 . The compound of  claim 37  having the structure: 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is —NR 5 —C(═0)-R 6  or —C(═O)—NR 5 R 6 ,
 wherein 
 R 5  is 
 
       
       
         
           
           
               
               
           
         
         
           R 6  is 
         
       
       
         
           
           
               
               
           
         
         
           
             wherein 
             X is a Cl, Br, or F; and 
             R 12  is H, C 1-5  alkyl, C 2-5  alkenyl, C 2-5  alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; 
           
         
         m is an integer from 0 to 2; 
         R 2  and R 3  are each, independently, H, halogen, —NH 2 , —CX 3 , —C(═O)OR 8 , C(═O)R 8 , —C(═O)NR 9 R 10 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, heteroalkyl, aryl, heteroaryl, or heterocyclyl;
 wherein 
 X is Cl, Br, or F; 
 R 8 , R 9  and R 10  are each, independently, H, C 1-5  alkyl, C 2-5  alkenyl, C 2-5  alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; 
 
         Ar 1  is 
       
       
         
           
           
               
               
           
         
         
           wherein X is a Cl, Br, or F; 
         
         Z is —O—, —S—, —CH 2 —, —C(O)—, —NH—, —NH—NH—, —NHC(═O)—, —C(═O)NH—, —NHC(═O)CH 2 NH— or —NHC(═O)CH═CH—; and 
         R 4  is —NH—OR 11 ,
 wherein R 11  is H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl, 
 
       
       or a pharmaceutically acceptable salt thereof. 
     
     
         39 . The compound of  claim 37 ,
 wherein m=1;   R 2  is H or CH 3 ; and   R 3  is H, CH 3 , Cl, Br, F, or CF 3 ,   
       or a pharmaceutically acceptable salt thereof. 
     
     
         40 . The compound of  claim 37 ,
 wherein R 4  is —NH—OR 11 ,
 wherein R 11  is H or CH 3 , 
   
       or a pharmaceutically acceptable salt thereof. 
     
     
         41 . The compound of  claim 37 ,
 wherein   R 5  is   
       
         
           
           
               
               
           
         
       
       and
 R 6  is 
 
       
         
           
           
               
               
           
         
       
       or a pharmaceutically acceptable salt thereof. 
     
     
         42 . The compound of  claim 37  having the structure: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       or a pharmaceutically acceptable salt thereof. 
     
     
         43 . A pharmaceutical composition comprising the compound of  claim 37  and a pharmaceutically acceptable carrier. 
     
     
         44 . A method of inhibiting the activity of a histone deactylase in a cell, the method comprising contacting the histone deacetylase with the compound of  claim 37  so as to inhibit the activity of the histone deacetylase; or of increasing accumulation of acetylated alpha tubulin in a cell, the method comprising contacting the cell with the compound of  claim 37  so as to increase the accumulation of acetylated alpha-tubulin in the cell. 
     
     
         45 . The compound of  claim 36  having the structure: 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is —NR 5 —C(═0)-R 6  or —C(═O)—NR 5 R 6 ,
 wherein 
 R 5  is 
 
       
       
         
           
           
               
               
           
         
         
           R 6  is 
         
       
       
         
           
           
               
               
           
         
         
           
             wherein 
             X is a Cl, Br, or F; and 
             R 12  is H, C 1-5  alkyl, C 2-5  alkenyl, C 2-5  alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; 
           
         
         m is an integer from 0 to 2; 
         R 2  and R 3  are each, independently, H, halogen, —NH 2 , —CX 3 , —C(═O)OR 8 , C(═O)R 8 , —C(═O)NR 9 R 10 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, heteroalkyl, aryl, heteroaryl, or heterocyclyl;
 wherein 
 X is Cl, Br, or F; 
 R 8 , R 9  and R 10  are each, independently, H, C 1-5  alkyl, C 2-5  alkenyl, C 2-5  alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; 
 
         Q is —Ar 1 —Z— or —Z—Ar 1 —Z—,
 wherein Ar 1  is 
 
       
       
         
           
           
               
               
           
         
         
           
             wherein X is a Cl, Br, or F; and 
           
           each occurrence of Z absent; and 
         
         R 4  is —NH—OR 11 ,
 wherein R 11  is H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl, 
 
       
       or a pharmaceutically acceptable salt thereof. 
     
     
         46 . The compound of  claim 45  having the structure: 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is —NR 5 —C(═0)-R 6  or —C(═O)—NR 5 R 6 ,
 wherein 
 R 5  is 
 
       
       
         
           
           
               
               
           
         
         
           R 6  is 
         
       
       
         
           
           
               
               
           
         
         
           
             wherein 
             X is a Cl, Br, or F; and 
             R 12  is H, C 1-5  alkyl, C 2-5  alkenyl, C 2-5  alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; 
           
         
         m is an integer from 0 to 2; 
         R 2  and R 3  are each, independently, H, halogen, —NH 2 , —CX 3 , —C(═O)OR 8 , C(═O)R 8 , —C(═O)NR 9 R 10 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, heteroalkyl, aryl, heteroaryl, or heterocyclyl;
 wherein 
 X is Cl, Br, or F; 
 R 8 , R 9  and R 10  are each, independently, H, C 1-5  alkyl, C 2-5  alkenyl, C 2-5  alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; 
 
         Ar 1  is 
       
       
         
           
           
               
               
           
         
         
           wherein X is a Cl, Br, or F; 
         
         Z absent; and 
         R 4  is —NH—OR 11 ,
 wherein R 11  is H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl, 
 
       
       or a pharmaceutically acceptable salt thereof. 
     
     
         47 . The compound of  claim 45 ,
 wherein m=1;   R 2  is H or CH 3 ; and   R 3  is H, CH 3 , Cl, Br, F, or CF 3 ,   
       or a pharmaceutically acceptable salt thereof. 
     
     
         48 . The compound of  claim 45 ,
 wherein R 4  is —NH—OR 11 ,
 wherein R 11  is H or CH 3 , 
   
       or a pharmaceutically acceptable salt thereof. 
     
     
         49 . The compound of  claim 45 ,
 wherein   R 5  is   
       
         
           
           
               
               
           
         
       
       and
 R 6  is 
 
       
         
           
           
               
               
           
         
       
       or a pharmaceutically acceptable salt thereof. 
     
     
         50 . A pharmaceutical composition comprising the compound of  claim 45  and a pharmaceutically acceptable carrier. 
     
     
         51 . A method of inhibiting the activity of a histone deactylase in a cell, the method comprising contacting the histone deacetylase with the compound of  claim 45  so as to inhibit the activity of the histone deacetylase; or of increasing accumulation of acetylated alpha tubulin in a cell, the method comprising contacting the cell with the compound of  claim 45  so as to increase the accumulation of acetylated alpha-tubulin in the cell. 
     
     
         52 . A compound having the structure: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       or a pharmaceutically acceptable salt thereof. 
     
     
         53 . A pharmaceutical composition comprising the compound of  claim 52  and a pharmaceutically acceptable carrier. 
     
     
         54 . A method of inhibiting the activity of a histone deactylase in a cell, the method comprising contacting the histone deacetylase with the compound of  claim 52  so as to inhibit the activity of the histone deacetylase; or of increasing accumulation of acetylated alpha tubulin in a cell, the method comprising contacting the cell with the compound of  claim 52  so as to increase the accumulation of acetylated alpha-tubulin in the cell.

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