US2012077779A1PendingUtilityA1

Inhibitors of Fibroblast Activation Protein Alpha

Individually held — no corporate assignee on recordPriority: Jul 5, 2005Filed: Jul 6, 2011Published: Mar 29, 2012
Est. expiryJul 5, 2025(expired)· nominal 20-yr term from priority
A61P 35/00C07F 5/025A61P 1/04C07D 277/06A61P 15/00A61P 11/00C07D 207/16C07F 5/04C07D 207/09
47
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Claims

Abstract

Disclosed are peptide-based compounds that include boronic acid or cyano functionality, which efficiently and selectively inhibit fibroblast activation protein alpha. Among other therapeutic utilities, the peptide-based compounds may be useful for the treatment of cancer.

Claims

exact text as granted — not AI-modified
1 . A compound having a structure of formula (I) 
       
         
           
           
               
               
           
         
       
       wherein
 L is absent or represents —XC(O)—; 
 R 1  is selected from the group consisting of H, C 1-6 alkyl, C 1-6 acyl, C 1-6 aralkyl, C 1-6 aracyl, C 1-6 heteroaracyl, carbocyclyl, aryl, and ArSO 2 —; 
 R 2  is selected from the group consisting of H and C 1-6 alkyl, or R 1  and R 2  together are phthaloyl, thereby forming a ring; 
 R 3  is selected from the group consisting of H, C 1-6 alkyl, C 1-6 hydroxyalkyl, C 1-6 thioalkyl, and C 1-6 aralkyl; 
 W is selected from the group consisting of B(Y 1 )(Y 2 ) and CN; 
 Y 1  and Y 2  are independently OH or a group that is hydrolyzable to a boronic acid, or together with the boron atom to which they are attached form a 5- to 8-membered ring that is hydrolyzable hydrolyzable to a boronic acid; and 
 X is selected from the group consisting of O and NH. 
 
     
     
         2 . The compound of  claim 1 , wherein R 3  is selected from the group consisting of H and C 1-6 alkyl. 
     
     
         3 . The compound of  claim 2 , wherein W is B(Y 1 )(Y 2 ); and R 3  is H. 
     
     
         4 . The compound of  claim 3 , wherein Y 1  and Y 2  are both OH. 
     
     
         5 . The compound of  claim 2 , wherein L is absent. 
     
     
         6 . The compound of  claim 5 , wherein R 1  and R 2  together are phthaloyl, thereby forming a ring. 
     
     
         7 . The compound of  claim 5 , wherein R 1  is selected from the group consisting of H, C 1-6 alkyl, C 1-6 acyl, C 1-6 aralkyl, C 1-6 aracyl, C 1-6 heteroaracyl, carbocyclyl, aryl, and ArSO 2 —. 
     
     
         8 . The compound of  claim 7 , wherein R 1  is H. 
     
     
         9 . The compound of  claim 7 , wherein R 1  is C 1-6 alkyl. 
     
     
         10 . The compound of  claim 9 , wherein R 1  is selected from the group consisting of methyl, ethyl, isopropyl, and tert-butyl. 
     
     
         11 . The compound of  claim 7 , wherein R 1  is C 1-6 acyl. 
     
     
         12 . The compound of  claim 11 , wherein R 1  is selected from the group consisting of acetyl and pivaloyl. 
     
     
         13 . The compound of  claim 7 , wherein R 1  is C 1-6 aralkyl. 
     
     
         14 . The compound of  claim 13 , wherein R 1  is phenylmethyl. 
     
     
         15 . The compound of  claim 7 , wherein R 1  is C 1-6 aracyl. 
     
     
         16 . The compound of  claim 15 , wherein R 1  is selected from the group consisting of 2-phenylethylcarbonyl, phenylmethylcarbonyl, (1-naphthyl)carbonyl, (2-naphthy)carbonyl, and (4-sulfamoylphenyl)carbonyl. 
     
     
         17 . The compound of  claim 7 , wherein R 1  is C 1-6 heteroaracyl. 
     
     
         18 . The compound of  claim 17 , wherein R 1  is pyrazyl. 
     
     
         19 . The compound of  claim 7 , wherein R 1  is carbocyclyl. 
     
     
         20 . The compound of  claim 19 , wherein R 1  is selected from the group consisting of cyclohexyl and adamantyl. 
     
     
         21 . The compound of  claim 7 , wherein R 1  is aryl. 
     
     
         22 . The compound of  claim 21 , wherein R 1  is phenyl. 
     
     
         23 . The compound of  claim 7 , wherein R 1  is ArSO 2 —. 
     
     
         24 . The compound of  claim 23 , wherein R 1  is phenylsulfonyl. 
     
     
         25 . The compound of  claim 4 , wherein L is —XC(O)—. 
     
     
         26 . The compound of  claim 25 , wherein X is O. 
     
     
         27 . The compound of  claim 26 , wherein R 1  is C 1-6 aralkyl. 
     
     
         28 . The compound of  claim 27 , wherein R 1  is phenylmethyl. 
     
     
         29 . The compound of  claim 25 , wherein X is NH. 
     
     
         30 . The compound of  claim 29 , wherein R 1  is selected from the group consisting of aryl and C 1-6 aralkyl. 
     
     
         31 . The compound of  claim 30 , wherein R 1  is aryl. 
     
     
         32 . The compound of  claim 31 , wherein R 1  is phenyl. 
     
     
         33 . The compound of  claim 30 , wherein R 1  is C 1-6 aralkyl. 
     
     
         34 . The compound of  claim 33 , wherein R 1  is phenylmethyl. 
     
     
         35 . A compound having a structure of formula (II) 
       
         
           
           
               
               
           
         
       
       wherein
 R 1  is selected from the group consisting of H, C 1-6 alkyl, C 1-6 acyl, C 1-6 aralkyl, C 1-6 aracyl, C 1-6 heteroaracyl, and carbocyclyl; 
 R 2  is selected from the group consisting of H and C 1-6 alkyl; 
 R 3  is selected from the group consisting of H, C 1-6 alkyl, C 1-6 hydroxyalkyl, C 1-6 thioalkyl, and C 1-6 aralkyl; 
 R 4  is selected from the group consisting of H and C 1-6 alkyl, or R 3  and R 4  together are C 1-6 alkyl, thereby forming a ring; 
 R 5  is selected from H, C 1-6 alkyl, C 1-6 hydroxyalkyl, C 1-6 thioalkyl, and C 1-6 aralkyl, or R 4  and R 5  together are C 1-6 alkyl-S; 
 W is selected from H, B(Y 1 )(Y 2 ), and CN; and 
 Y 1  and Y 2  are independently OH or a group that is hydrolyzable to a boronic acid, or together with the boron atom to which they are attached form a 5- to 8-membered ring that is hydrolyzable to a boronic acid; 
 with the proviso that when W is H, R 4  and R 5  together are C 1-6 alkyl-S—C 1-6 alkyl. 
 
     
     
         36 . The compound of  claim 35 , wherein R 1  is selected from the group consisting of C 1-6 acyl and C 1-6 aracyl; R 3  and W are H; and R 4  and R 5  together are C 1-6 alkyl-S—C 1-6 alkyl, thereby forming a ring. 
     
     
         37 . The compound of  claim 36 , wherein R 4  and R 5  together are C 2 alkyl-S—C 1 alkyl, thereby forming a five-membered ring. 
     
     
         38 . The compound of  claim 35 , wherein R 1  is selected from the group consisting of C 1-6 acyl and C 1-6 aracyl; and R 3  and R 4  together are C 1-6 alkyl, thereby forming a ring. 
     
     
         39 . The compound of  claim 38 , wherein R 3  and R 4  together are C 3 alkyl, thereby forming a five-membered ring. 
     
     
         40 . The compound of  claim 35 , wherein R 3  and R 5  are selected from the group consisting of H and C 1-6 alkyl. 
     
     
         41 . The compound of  claim 40 , wherein W is B(Y 1 )(Y 2 ). 
     
     
         42 . The compound of  claim 41 , wherein Y 1  and Y 2  are both OH. 
     
     
         43 . The compound of  claim 42 , wherein R 1  is selected from the group consisting of C 1-6 acyl and C 1-6 aracyl; R 2  and R 4  are H; and R 3  and R 5  are C 1-6 alkyl. 
     
     
         44 . The compound of  claim 43 , wherein R 1  is C 1-6 acyl. 
     
     
         45 . The compound of  claim 44 , wherein R 1  is acetyl. 
     
     
         46 . The compound of  claim 43 , wherein R 1  is C 1-6 aracyl. 
     
     
         47 . The compound of  claim 46 , wherein R 1  is selected from the group consisting of phenylcarbonyl and (1-naphthyl)carbonyl. 
     
     
         48 . A method for treating cancer, comprising administering to a mammal in need thereof a therapeutically effective amount of a compound of  claim 1 . 
     
     
         49 . The method of  claim 48 , wherein the cancer is selected from human epithelial cancer and soft tissue carcinoma. 
     
     
         50 . The method of  claim 49 , wherein the cancer is human epithelial cancer selected from the group consisting of breast cancer, non-small-cell lung cancer, and colorectal cancer. 
     
     
         51 . A pharmaceutical composition, comprising a compound of  claim 1 ; and a pharmaceutically acceptable diluent or carrier. 
     
     
         52 - 54 . (canceled) 
     
     
         55 . A method for treating cancer, comprising administering to a mammal in need thereof a therapeutically effective amount of a compound of  claim 35 . 
     
     
         56 . The method of  claim 55 , wherein the cancer is selected from human epithelial cancer and soft tissue carcinoma. 
     
     
         57 . The method of  claim 56 , wherein the cancer is human epithelial cancer selected from the group consisting of breast cancer, non-small-cell lung cancer, and colorectal cancer. 
     
     
         58 . A pharmaceutical composition, comprising a compound of  claim 35 ; and a pharmaceutically acceptable diluent or carrier.

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