US2013130968A1PendingUtilityA1

Compounds for enzyme inhibition

Assignee: Onyx TherapeuticsPriority: Nov 9, 2005Filed: Jan 8, 2013Published: May 23, 2013
Est. expiryNov 9, 2025(expired)· nominal 20-yr term from priority
A61P 37/00A61P 37/02A61P 43/00A61P 25/28A61P 35/00A61P 25/00A61P 31/12A61P 29/00A61P 31/18A61P 31/00A61P 21/00C07K 5/06139C07K 5/0606C07K 5/0808A61K 31/69C07K 5/06026C07K 5/0812A61K 45/06C07K 5/0821C07K 5/0806A61K 38/55A61K 38/00C07K 5/06034C07K 5/1024C07K 5/081C07K 5/06078C07K 5/08A61K 38/06C07K 5/06
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Claims

Abstract

Peptide-based compounds including heteroatom-containing, three-membered rings efficiently and selectively inhibit specific activities of N-terminal nucleophile (Ntn) hydrolases associated with the proteasome. The peptide-based compounds include an epoxide or aziridine, and functionalization at the N-terminus. Among other therapeutic utilities, the peptide-based compounds are expected to display anti-inflammatory properties and inhibition of cell proliferation. Oral administration of these peptide-based proteasome inhibitors is possible due to their bioavailability profiles.

Claims

exact text as granted — not AI-modified
1 . A method for the treatment of an immune-related condition in a patient, comprising administering to the patient a therapeutically effective amount of a pharmaceutical composition comprising a compound having a structure of formula (I) or a pharmaceutically acceptable salt thereof: 
       
         
           
           
               
               
           
         
         wherein 
         L is selected from C═O and C═S; 
         X is selected from O, S, NH, and N—C 1-6 alkyl; 
         Z is absent, C 1-6  alkyl, or C 1-6 alkoxy; 
         R 1 , R 2 , and R 3  are each independently selected from hydrogen, C 1-6  alkyl, C 1-6  alkenyl, C 1-6  alkynyl, C 1-6  hydroxyalkyl, C 1-6  alkoxyalkyl, aryl, C 1-6  aralkyl, heteroaryl, heterocyclyl, C 1-6  heterocycloalkyl, C 1-6  heteroaralkyl, carbocyclyl, and C 1-6  carbocyclolalkyl; 
         R 4  is selected from hydrogen, C 1-6  aralkyl, and C 1-6  alkyl; 
         R 5  is heteroaryl; and 
         R 6  and R 7  are independently selected from hydrogen, C 1-6  alkyl, and C 1-6  aralkyl and a pharmaceutically acceptable diluent or carrier. 
       
     
     
         2 . The method of  claim 1 , wherein Z is absent. 
     
     
         3 . The method of  claim 1 , wherein R 4 , R 6 , and R 7  are independently selected from hydrogen and methyl. 
     
     
         4 . The method of  claim 1 , wherein L is C═O. 
     
     
         5 . The method of  claim 1 , wherein R 1 , R 2 , and R 3  are independently selected from hydrogen, C 1-6 alkyl, C 1-6  alkenyl, C 1-6  alkynyl, C 1-6  hydroxyalkyl, C 1-6  alkoxyalkyl, C 1-6  aralkyl, C 1-6  heterocycloalkyl, C 1-6  heteroaralkyl, and C 1-6  carbocyclolalkyl. 
     
     
         6 . The method of  claim 5 , wherein any of R 1 , R 2 , and R 3  are independently C 1-6  alkyl. 
     
     
         7 . The method of  claim 6 , wherein any of R 1 , R 2 , and R 3  are independently selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and isobutyl. 
     
     
         8 . The method of  claim 7 , wherein any of R 1 , R 2 , and R 3  are independently propargyl. 
     
     
         9 . The method of  claim 5 , wherein any of R 1 , R 2 , and R 3  are independently C 1-6  hydroxyalkyl. 
     
     
         10 . The method of  claim 9 , wherein any of R 1 , R 2 , and R 3  are independently selected from hydroxymethyl and hydroxyethyl. 
     
     
         11 . The method of  claim 5 , wherein any of R 1 , R 2 , and R 3  are independently C 1-6  alkoxyalkyl. 
     
     
         12 . The method of  claim 11 , wherein any of R 1 , R 2 , and R 3  are independently selected from methoxymethyl and methoxyethyl. 
     
     
         13 . The method of  claim 5 , wherein any of R 1 , R 2 , and R 3  are independently C 1-6  heteroaralkyl. 
     
     
         14 . The method of  claim 13 , wherein any of R 1 , R 2 , and R 3  are independently selected from imidazolylmethyl, pyrazolylmethyl, and thiazolylmethyl, and pyridylmethyl. 
     
     
         15 . The method of  claim 5 , wherein any of R 1 , R 2 , and R 3  are independently cyclohexylmethyl. 
     
     
         16 . The method of  claim 1 , wherein R 1 , R 2 , and R 3  are all different. 
     
     
         17 . The method of  claim 1 , wherein at least one of R 1  and R 2  is selected from C 1-6  hydroxyalkyl and C 1-6  alkoxyalkyl. 
     
     
         18 . The method of  claim 17 , wherein at least one of R 1  and R 2  is C 1-6  alkoxyalkyl. 
     
     
         19 . The method of  claim 18 , wherein at least one of R 1  and R 2  is selected from methoxymethyl and methoxyethyl. 
     
     
         20 . The method of  claim 19 , wherein R 3  is selected from C 1-6  alkyl and C 1-6  aralkyl. 
     
     
         21 . The method of  claim 20 , wherein R 3  is C 1-6  alkyl. 
     
     
         22 . The method of  claim 21 , wherein R 3  is selected from methyl, ethyl, isopropyl, sec-butyl, and isobutyl. 
     
     
         23 . The method of  claim 22 , wherein R 3  is isobutyl. 
     
     
         24 . The method of  claim 20 , wherein R 3  is C 1-6  aralkyl. 
     
     
         25 . The method of  claim 24 , wherein R 3  is phenylmethyl. 
     
     
         26 . The method of  claim 1 , wherein R 5  is 5- or 6-membered heteroaryl. 
     
     
         27 . The method of  claim 26 , wherein R 5  is selected from isoxazole, isothiazole, furan, thiophene, oxazole, thiazole, pyrazole, or imidazole. 
     
     
         28 . The method of  claim 27 , wherein R 5  is selected from isoxazole, furan, or thiophene. 
     
     
         29 . The method of  claim 28 , wherein R 5  is furan or thiophene. 
     
     
         30 . The method of  claim 29 , wherein R 5  is unsubstituted furan-3-yl or thien-2-yl. 
     
     
         31 . The method of  claim 28 , wherein R 5  is isoxazol-3-yl or isoxazol-5-yl. 
     
     
         32 . The method of  claim 31 , wherein R 5  is isoxazol-3-yl that has a substituent at the 5-position. 
     
     
         33 . The method of  claim 31 , wherein R 5  is isoxazol-5-yl that has a substituent at the 3-position. 
     
     
         34 . The method of  claim 32  or  33 , wherein the substituent is selected from C 1-6  alkyl, C 1-6  alkoxy, C 1-6  alkoxyalkyl, C 1-6  hydroxyalkyl, carboxylic acid, aminocarboxylate, C 1-6  alkylaminocarboxylate, (C 1-6  alkyl) 2 aminocarboxylate, C 1-6  alkylcarboxylate, C 1-6  heteroaralkyl, C 1-6  aralkyl, C 1-6  heterocycloalkyl, and C 1-6  carbocycloalkyl. 
     
     
         35 . The method of  claim 34 , wherein the substituent is selected from methyl, ethyl, isopropyl, and cyclopropylmethyl. 
     
     
         36 . The method of  claim 32  or  33 , wherein the substituent is selected from C 1-6 heteroaralkyl and C 1-6 heterocycloalkyl. 
     
     
         37 . The method of  claim 36 , wherein the substituent is 1,2,4-triazol-5-ylmethyl. 
     
     
         38 . The method of  claim 36 , wherein the substituent is azetidin-1-ylmethyl. 
     
     
         39 . The method of  claim 36 , wherein the substituent is 
       
         
           
           
               
               
           
         
         wherein W is O, NR, or CH 2 , and R is H or C 1-6  alkyl. 
       
     
     
         40 . The method of  claim 39 , wherein W is O. 
     
     
         41 . The method of  claim 32  or  33 , wherein the substituent is selected from C 1-6  alkoxy and C 1-6  alkoxyalkyl. 
     
     
         42 . The method of  claim 41 , wherein the substituent is selected from methoxy, ethoxy, methoxymethy, and methoxyethyl. 
     
     
         43 . The method of  claim 32  or  33 , wherein the substituent is selected from carboxylic acid, aminocarboxylate, C 1-6  alkylaminocarboxylate, (C 1-6  alkyl) 2 aminocarboxylate, or C 1-6  alkylcarboxylate. 
     
     
         44 . The method of  claim 43 , wherein the substituent is methyl carboxylate. 
     
     
         45 . The method of  claim 1 , wherein the compound is selected from: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         or a pharmaceutically acceptable salt thereof. 
       
     
     
         46 . The method of  claim 1 , wherein the immune-related condition is selected from the group consisting of: allergy, asthma, graft-versus-host disease, and an auto-immune disease. 
     
     
         47 . The method of  claim 46 , wherein the immune-related condition is graft-versus-host disease. 
     
     
         48 . The method of  claim 1 , wherein the method further comprises administration of one or more other proteasome inhibitor(s). 
     
     
         49 . The method of  claim 48 , wherein at least one of the one or more other proteasome inhibitor(s) is bortezomib. 
     
     
         50 . The method of  claim 1 , wherein the pharmaceutical composition is orally bioavailable. 
     
     
         51 . A method for treating an immune-related condition in a patient comprising administering to the patient a pharmaceutical composition comprising a compound having the structure: 
       
         
           
           
               
               
           
         
         or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable diluent or carrier. 
       
     
     
         52 . The method of  claim 51 , wherein the pharmaceutical composition is orally bioavailable. 
     
     
         53 . The method of  claim 51 , wherein the immune-related condition is selected from the group consisting of: allergy, asthma, graft-versus-host disease, and an auto-immune disease. 
     
     
         54 . The method of  claim 53 , wherein the immune-related condition is graft-versus-host disease. 
     
     
         55 . The method of  claim 51 , wherein the method further comprises administration of one or more other proteasome inhibitor(s). 
     
     
         56 . The method of  claim 55 , wherein at least one of the one or more other proteasome inhibitor(s) is bortezomib.

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