US2023265041A1PendingUtilityA1

Curcumin analogues as zinc chelators and tehir uses

86
Assignee: JOHNSON FRANCISPriority: May 15, 2009Filed: Feb 27, 2023Published: Aug 24, 2023
Est. expiryMay 15, 2029(~2.8 yrs left)· nominal 20-yr term from priority
C07C 69/738C07C 49/255C07C 225/22C07C 235/78C07C 235/80C07C 237/20C07D 213/50C12N 9/6491C12Y 304/24A61P 39/04
86
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Claims

Abstract

This invention provides a compound having the structure wherein α, β, X, Y, and R 1 -R 11 are defined herein. This invention also provides a pharmaceutical composition comprising the above compounds, a method of inhibiting the activity and/or levels of a matrix metalloproteinase (MMP), a method of inhibiting the production of a cytokine in a population of cells, a method of inhibiting the production of a growth factor in a population of cells, and a method of inhibiting NF K -B activation in a population of cells.

Claims

exact text as granted — not AI-modified
1 . A compound having the structure 
       
         
           
           
               
               
           
         
       
       wherein
 bond α and β are each, independently, present or absent; 
 X is CR 5  or N; Y is CR 10  or N; 
 R 1  is H, CF 3 , halogen, —NO 2 , —OCF 3 , —OR 12 , —NHCOR 12 , —SR 12 , —SO 2 R 13 , —COR 14 , —CSR 14 , —C (═NR 12 ) R 14 , —C (═NH) R 14 , —SOR 12 , —POR 12 , —P (═0) (OR 12 ) (OR 13 ), or —P (OR 12 ) (OR 13 ),
 wherein R 12  and R 13  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 R 14  is C 2-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, heteroaryl, 
 heterocyclyl, methoxy, —OR 15 , -NR 16 R 17 , or
                     
 wherein R 15  is H, C 3-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl; 
 R 16  and R 17  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 R 1S , R 19 , R 21 , and R 22  are each independently H, halogen, —NO 2 , —CN, —NR 23 R 24 , —SR 23 , —SO 2 R 23 , —CO 2 R 23 , —OR 25 , CF 3 , —SOR 23 , —POR 23 , —C (═S) R 23 , —C (═NH) R 23 , —C (═NR 24 ) R 23 , —C (═N) R 23 , —P (═O) (OR 23 ) (OR 24 ), —P (OR 23 ) (OR 24 ), —C (═S) R 23 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 wherein R 23 , R 24 , and R 25  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 
 R 20  is halogen, —NO 2 , —CN, -NR 26 R 27 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl;
 wherein R 26  and R 27  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 
 
 R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R e , R 9 , R 10 , and R 11  are each independently, H, halogen, —NO 2 , —CN, —NR 28 R 29 , —NHR 28 R 29   + , —SR 28 , —SO 2 R 28 , —OR 28 , —CO 2 R 28 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl;
 wherein R 28  and R 29  are each, H, CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-   10  alkynyl, or -C(=O)-heterocyclyl; and 
 
 wherein when R 1  is H, R 3 , R 4 , R 5 , R 8 , R 9 , or R 10 , is halogen, —NO 2 , —CN, —NR 28 R 29 , —NHR 28 R 29   + , —SR 28 , —SO 2 R 28 , —CO 2 R 28 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl;
 wherein R 28  and R 29  are each, H, CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2 - 10  alkynyl, or heterocyclyl; and 
 
 wherein each occurrence of alkyl, alkenyl, or alkynyl is branched or unbranched, unsubstituted or substituted; 
 or a salt thereof. 
 
     
     
         2 . The compound of  claim 1 , wherein when R 1  is H, R 3 , R 4 , R 5 , R 8 , R 9 , or R 10 , is —NO 2 , —NR 28 R 29 , —NHR 28 R 29   + , —SR 28 , —SO 2 R 28 , —CO 2 R 28 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl; or a salt thereof, or
 wherein when R 1  is H, R 4  or R 9  is —NO 2 , —NR 28 R 29 , —NHR 28 R 29   + ; or a salt thereof, 
 wherein when R 1  is H, R 4  or R 9  is -NR 28 R 29  or —NHR 28 R 29   + ; or a salt thereof. 
 
     
     
         3 - 4 . (canceled) 
     
     
         5 . The compound of  claim 1 , wherein
 R 1  is H or —COR 14 ,
 wherein R 14  is methoxy or -NH-phenyl; 
   R 2 , R 5 , R 6 , R 7 , R 10  and R 11  are each H;   R 3 , R 4 , R 8 , and R 9  are each, independently H, —OH, —OCH 3 , -N (CH 3 )  2  or —NH (CH 3 )  2   + ;   or a salt thereof.   
     
     
         6 . The compound of  claim 1 , having the structure 
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
       or a salt thereof. 
     
     
         7 . The compound of  claim 1  having the structure 
       
         
           
           
               
               
           
         
       
       wherein
 bond α and β are each, independently, present or absent; 
 R 1  is CF 3 , halogen, —NO 2 , —OCF 3 , —OR 12 , —NHCOR 12 , —SR 12 , —SO 2 R 13 , —COR 14 , —CSR 14 , or —CNR 14 ,
 wherein R 12  and R 13  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 R 14  is C 2-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, heteroaryl, 
 heterocyclyl, methoxy, —OR 15 , —NR 16 R 17 , or
                     
 wherein R 15  is H, C 3-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl; 
 R 16  and R 17  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 R 1S , R 19 , R 21 , and R 22  are each independently H, halogen, —NO 2 , —CN, —NR 23 R 24 , —SR 23 , —SO 2 R 23 , —CO 2 R 23 , —OR 25 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 wherein R 23 , R 24 , and R 25  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 R 20  is halogen, —NO 2 , —CN, —NR 26 R 27 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 wherein R 26  and R 27  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 
 
 R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11  are each independently, H, halogen, —NO 2 , —CN, —NR 28 R 29 , —SR 28 , —SO 2 R 28 , —OR 28 , —CO 2 R 28 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl;
 wherein R 28  and R 29  are each, H, CF 3 , C 1-10  alkyl, C 2-10  alkenyl, or C 2-10  alkynyl; and 
 
 wherein each occurrence of alkyl, alkenyl, or alkynyl is branched or unbranched, unsubstituted or substituted; and 
 wherein at least one of R 2 , R 3 , R 4 , R 5 , and R 6  and at least one of R 7 , R 8 , R 9 , R 10 , and R 11 , are each, independently, —OR 28 ; 
 or a salt thereof. 
 
     
     
         8 . The compound of  claim 7  having the structure
                     
 wherein R 1  is CF 3 , halogen, —NO 2 , —OCF 3 , —OR 12 , —NHCOR 12 , —SR 12 , —SO 2 R 13 , —COR 14 , —CSR 14 , or —CNR 14 ,
 wherein R 12  and R 13  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 R 14  is C 2-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, heteroaryl, 
 heterocyclyl, methoxy, —OR 15 , —NR 16 R 17 , or
                     
 wherein R 15  is H, C 3-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl; 
 R 16  and R 17  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 R 1S , R 19 , R 21 , and R 22  are each independently H, halogen, —NO 2 , —CN, —NR 23 R 24 , —SR 23 , —SO 2 R 23 , —CO 2 R 23 , —OR 25 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 wherein R 23 , R 24 , and R 25  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 R 20  is halogen, —NO 2 , —CN, —NR 26 R 27 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 wherein R 26  and R 27  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 
 
 R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11  are each independently, H, halogen, —NO 2 , —CN, —NR 28 R 29 , —SR 28 , —SO 2 R 28 , —OR 28 , —CO 2 R 28 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl;
 wherein R 28  and R 29  are each, H, CF 3 , C 1-10  alkyl, C 2-10  alkenyl, or C 2-10  alkynyl; and 
 
 wherein each occurrence of alkyl, alkenyl, or alkynyl is branched or unbranched, unsubstituted or substituted; and 
 wherein at least one of R 2 , R 3 , R 4 , R 5 , and R 6  and at least one of R 7 , R 8 , R 9 , R 10 , and R 11 , are each, independently, —OR 28 ; 
 or a salt thereof. 
 
     
     
         9 . The compound of  claim 8  having the structure
                     
 wherein R 14  is C 2-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, heteroaryl, 
 heterocyclyl, methoxy, —OR 15 , —NR 16 R 17 , or
                     
 wherein R 15  is H, C 3-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl; 
 R 16  and R 17  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 R 1S , R 19 , R 21 , and R 22  are each independently H, halogen, —NO 2 , —CN, —NR 23 R 24 , —SR 23 , —SO 2 R 23 , —CO 2 R 23 , —OR 25 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl;
 wherein R 23 , R 24 , and R 25  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 
 R 20  is halogen, —NO 2 , —CN, —NR 26 R 27 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl;
 wherein R 26  and R 27  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 
 
 R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11  are each independently, H, halogen, —NO 2 , —CN, —NR 28 R 29 , —SR 28 , —SO 2 R 28 , —OR 28 , —CO 2 R 28 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl;
 wherein R 28  and R 29  are each, H, CF 3 , C 1-10  alkyl, C 2-10  alkenyl, or C 2-10  alkynyl; and 
 
 wherein each occurrence of alkyl, alkenyl, or alkynyl is branched or unbranched, unsubstituted or substituted; and 
 wherein at least one of R 2 , R 3 , R 4 , R 5 , and R 6  and at least one of R 7 , R 8 , R 9 , R 10 , and R 11 , are each, independently, —OR 28 ; 
 or a salt thereof. 
 
     
     
         10 . The compound of  claim 9  having the structure
                     
 wherein R 14  is C 2-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, heteroaryl, 
 heterocyclyl, methoxy, —OR 15 , —NR 16 R 17 , or
                     
 wherein R 15  is H, C 3-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl; 
 R 16  and R 17  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 R 1S , R 19 , R 21 , and R 22  are each independently H, halogen, —NO 2 , —CN, -NR 23 R 24 , —SR 23 , —SO 2 R 23 , —CO 2 R 23 , —OR 25 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl;
 wherein R 23 , R 24 , and R 25  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 
 R 20  is halogen, —NO 2 , —CN, —NR 26 R 27 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl;
 wherein R 26  and R 27  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 
 
 R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11  are each independently, H, halogen, —NO 2 , —CN, —NR 28 R 29 , —SR 28 , —SO 2 R 28 , —OR 28 , —CO 2 R 28 , CF 3 ;
 wherein R 28  and R 29  are each, H, CF 3 , C 1-5  alkyl, C 2-5  alkenyl, or C 2-5  alkynyl; and 
 
 wherein each occurrence of alkyl, alkenyl, or alkynyl is branched or unbranched, unsubstituted or substituted; and 
 wherein at least one of R 2 , R 3 , R 4 , R 5 , and R 6  and at least one of R 7 , R 8 , R 9 , R 10 , and R 11 , are each, independently, —OR 28 ; 
 or a salt thereof. 
 
     
     
         11 . The compound of  claim 8  wherein R 14  is methoxy,
 —OR 15  or —NR 16 R 17 ,
 wherein R 15  is H, C 3-10  alkyl, C 2-10  alkenyl, or C 2-10  alkynyl; 
 R 16  and R 17  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 or a salt thereof, or 
 wherein R 14  is methoxy or -NR 16 R 17 , 
 wherein R 16  and R 17  are each, independently, H, C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl; 
 or a salt thereof, or 
 wherein R 14  is —OR 15 , wherein R 15  is H, C 3-10  alkyl, C 2-10  alkenyl, or C 2-10  alkynyl; or a salt thereof, or 
 wherein R 14  is -NR 16 R 17 , 
 wherein R 16  and R 17  are each, independently, H or aryl; 
 R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11  are each independently, H, -NR 28 R 29 , or —OR 28 , 
 wherein R 28  and R 29  are each, H or C 1-10  alkyl; 
 or a salt thereof, or 
 wherein R 14  is —NH—phenyl; 
 R 2 , R 5 , R 6 , R 7 , R 10 , and R 11  are each H; 
 R 3 , R 4 , R 8 , and R 9  are each, independently, H, —OH, or —OCH 3 ; or a salt thereof. 
 
 
     
     
         12 - 15 . (canceled) 
     
     
         16 . The compound of claim  15  having the structure: 
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
       or a salt thereof. 
     
     
         17 . The compound of  claim 11  having the structure
                     
 wherein R 3 , R 4 , R 8 , and R 9  are H, —OCH 3 , or —OH; R 14  is methoxy or —N(CH 3 ) 2 ; or a salt thereof. 
 
     
     
         18 . The compound of  claim 17  having the structure 
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
       or a salt thereof. 
     
     
         19 . The compound of  claim 11  wherein R 14  is methoxy;
 R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11  are each, independently, H, —OH, —OCH 3 , —NO 2 , or —CO 2 CH 3 ; or a salt thereof. 
 
     
     
         20 . The compound of  claim 19  having the structure 
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
       
       or a salt thereof. 
     
     
         21 . The compound of  claim 1 , wherein X is N and/or α and β are both present; or a salt thereof. 
     
     
         22 . (canceled) 
     
     
         23 . The compound of  claim 19  having the structure: 
       
         
           
           
               
               
           
         
       
       or a salt thereof. 
     
     
         24 . A pharmaceutical composition comprising a pharmaceutically acceptable carrier and the compound of  claim 1 . 
     
     
         25 . A method of inhibiting the activity and/or levels of a matrix metalloproteinase (MMP) or inhibiting the production of a cytokine in a population of mammalian cells or inhibiting the production of a growth factor in a population of mammalian cells or inhibiting NF K -B activation in a population of cells comprising contacting the matrix metalloproteinase or a cell producing an MMP or MMPs or the population of cells with the compound of  claim 1  so as to inhibit the activity of a matrix metalloproteinase. 
     
     
         26 - 34 . (canceled) 
     
     
         35 . A method of increasing water solubility, metal binding ability, MMP inhibition activity, cytokine inhibition activity, growth factor inhibition activity, or NF K B activation inhibition activity of curcumin comprising synthesizing a compound having the structure 
       
         
           
           
               
               
           
         
       
       wherein 
 bond α and β are each, independently, present or absent; 
 X is CR 5  or N; Y is CR 10  or N; 
 R 1  is H or an electron-withdrawing group; 
 R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11  are each independently, H, halogen, —NO 2 , —CN, —NR 28 R 29 , —NHR 28 R 29   + , —SR 28 , —SO 2 R 28 , —OR 28 , —CO 2 R 28 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl;
 wherein R 28  and R 29  are each, H, CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-   10  alkynyl, or -C(=O)-heterocyclyl; and 
 
 wherein when R 1  is H, R 3 , R 4 , R 5 , R 8 , R 9 , or R 10 , is halogen, —NO 2 , —CN, -NR 28 R 29 , —NHR 28 R 29 +, —SR 28 , —SO 2 R 28 , —CO 2 R 28 , CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-10  alkynyl, aryl, heteroaryl, or heterocyclyl;
 wherein R 28  and R 29  are each, H, CF 3 , C 1-10  alkyl, C 2-10  alkenyl, C 2-   10  alkynyl, or -C(=O)-heterocyclyl; and 
 
 wherein each occurrence of alkyl, alkenyl, or alkynyl is branched or unbranched, unsubstituted or substituted; 
 or a salt thereof. 
 
     
     
         36 - 37 . (canceled) 
     
     
         38 . The method of  claim 35 , wherein the compound synthesized has the structure
                       wherein R 1  is an electron-withdrawing group, or a salt thereof.

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