US2013302282A1PendingUtilityA1

Inhibitors of Hepatitis C Virus

55
Assignee: ZHONG MINPriority: Oct 26, 2010Filed: Oct 21, 2011Published: Nov 14, 2013
Est. expiryOct 26, 2030(~4.3 yrs left)· nominal 20-yr term from priority
A61P 31/12A61P 31/00A61P 43/00A61P 31/14A61P 1/16C07D 491/14A61K 31/343A61K 31/4355A61K 31/437A61K 38/212C07D 498/04C07D 491/048C07D 307/84A61K 31/55C07D 487/04A61K 31/553A61K 31/407A61K 31/5513A61K 31/7056A61K 45/06C07D 471/14C07D 491/04A61K 31/4741C07D 471/04
55
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Claims

Abstract

A class of compounds that inhibit Hepatitis C Virus (HCV) is disclosed, along with compositions containing the compound, and methods of using the composition for treating individuals infected with HCV.

Claims

exact text as granted — not AI-modified
It is claimed: 
     
         1 . A compound having the structural formula I: 
       
         
           
           
               
               
           
         
         wherein, 
         L 1 , L 2  and L 3  together with the attached carbons of the aromatic ring to form a 5-12 member ring, containing 0-4 heteroatoms of N, O, S, P and/or Si; and 
         L 1 , L 2 , or L 3  is independently selected from the group consisting of a bond, —O—, —C(R 15 R 16 )—, —NR 3 —, —S(O) n —, —P(O)—, —Si(R 4 R 5 )—, —C(O)—, —C(O)O—, and substituted alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycle, aryl, heteroaryl, amide, carbamate, urea, and sulfonamide; 
         n is 0, 1, or 2; 
         U or V is independently CH, N, CF, CCl, or CCN; 
         W, X, or Z is independently C or N; 
         Y is NR N , N, O, S, Se, or —CR a R b ; 
         R N  is hydrogen, C 1-4  alkyl, C 3-6  cycloalkyl, C 4-5  heterocycle, aryl, heteroaryl, amide, sulfonamide, or carbamate; 
         R a , R b  is independently hydrogen, methyl, or together to form a C 3-6  cycloalkyl bearing 0-1 heteroatom of O or NR 3 ; 
         R 1  is selected from hydrogen, halide, —CF 3 , —CN, —C(O)H, —C(O)OR 6 —, —C(O)NHR 7 , —C(O)N(OH)R 7 , —C(═NOMe)NHR 7 , C(═NOH)NHR 7 , —C(CF 3 )NHR 8 , —C(CN)NHR 9 , —S(O) 2 NHR 10 , —C(═NCN)NHR 11 , 
       
       
         
           
           
               
               
           
         
         R 2  is a substituted or unsubstituted aryl or heteroaryl; 
         R 3  is selected from the group of hydrogen, alkylcarbonyl, cycloalkylcarbonyl, alkoxylcarbonyl, cycloalkoxycarbonyl, alkylsulfonyl and cycloalkylsulfonyl; 
         R 4  and R 5  are independently methyl, ethyl, or cyclopropyl; 
         R 6  is hydrogen, allyl, C 1-4  alkyl, cyclopropyl, or benzyl; 
         R 7  is hydrogen, C 1-4  alkyl, cyclopropyl, alkoxy, cyclopropoxy, alkylsulfonyl, or cycloalkylsulfonyl; 
         R 8 , R 9 , R 10 , or R 11  is independently hydrogen, C 1-4  alkyls, cyclopropyl, C 1-4  alkoxys, or cyclopropoxy; and 
         R 15 , R 16  is independently hydrogen, hydroxyl, azide, C 2-4  alkenyl, C 2-4  alkynyl, C 1-4  alkyl, cyclopropyl, C 1-4  alkoxy, or cyclopropoxy or R 15  and R 16  together are a carbonyl or C 1-4  alkenylidene or R 15  and R 16  joined together with the attached carbon are 3-6 member ring optionally containing 0-3 heteroatoms of O, NR N  and/or S. 
       
     
     
         2 . The compound of  claim 1 , having an inhibitory activity with respect to HCV, as measured by the concentration of the compound effective to produce a half-maximal inhibition of HCV1b replication (EC 50 ) in a 1b_Huh-Luc/Neo-ET cell line in culture, of 1 mM or less. 
     
     
         3 . The compound of  claim 1 , wherein 
       
         
           
           
               
               
           
         
       
       together with the attached carbons of the aromatic ring is a seven- or eight-member ring. 
     
     
         4 . The compound of  claim 1 , wherein 
       
         
           
           
               
               
           
         
       
       together with the attached carbons of the aromatic ring to form a 5-9 member ring, L 1  is —C(R 15 R 16 )—, and L 3  is —N(SO 2 Me)- or —O—, where
 R 15 , R 16  is independently hydrogen, hydroxyl, azide, C 2-4  alkenyl, C 2-4  alkynyl, C 1-4  alkyl, cyclopropyl, C 1-4  alkoxy, or cyclopropoxy or R 15  and R 16  together are a carbonyl or C 1-4  alkenylidene or R 15  and R 16  joined together with the attached carbon are 3-6 member ring optionally containing 0-3 heteroatoms of O, NR N  and/or S. 
 
     
     
         5 . The compound of  claim 1 , having the structure: 
       
         
           
           
               
               
           
         
         wherein, 
         L 1 , L 2  and —N(SO 2 Me)- together with the attached carbons of the aromatic ring to form a 5-12 member ring, containing 1-4 heteroatoms of N, O, S, P and/or Si; 
         L 1  or L 2  is independently selected from the group consisting of a bond, —O—, —C(R 15 R 16 )—, —NR 3 —, —S(O) n —, —P(O)—, —Si(R 4 R 5 )—, —C(O)O—, and substituted alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycle, aryl, heteroaryl, amide, carbamate, urea, and sulfonamide; 
         n is 0, 1, or 2; and 
         R 1  is selected from hydrogen, halide, —CF 3 , —CN, —C(O)H, —C(O)OR 6 —, —C(O)NHR 7 , —C(O)N(OH)R 7 , —C(═NOMe)NHR 7 , C(═NOH)NHR 7 , —C(CF 3 )NHR 8 , —C(CN)NHR 9 , —S(O) 2 NHR 10 , —C(═NCN)NHR 11 , 
       
       
         
           
           
               
               
           
         
         R 2  is an aryl or heteroaryl having one or more R 17  substituents; 
         R 3  is selected from the group of hydrogen, alkylcarbonyl, cycloalkylcarbonyl, alkoxylcarbonyl, cycloalkoxycarbonyl, alkyl sulfonyl and cycloalkylsulfonyl; 
         R 4  and R 5  are independently methyl, ethyl, or cyclopropyl; 
         R 15 , R 16  is independently hydrogen, hydroxyl, azide, C 2-4  alkenyl, C 2-4  alkynyl, C 1-4  alkyl, cyclopropyl, C 1-4  alkoxy, or cyclopropoxy or R 15  and R 16  together are a carbonyl or C 1-4  alkenylidene or R 15  and R 16  joined together with the attached carbon are 3-6 member ring optionally containing 0-3 heteroatoms of O, NR N  and/or S; and 
         R 17  is H, F, Cl or CN. 
       
     
     
         6 . The compound of  claim 5 , wherein 
       
         
           
           
               
               
           
         
       
       is selected from the group consisting 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         R 1  is selected from the group consisting of 
       
       
         
           
           
               
               
           
         
       
       and R 2  is selected from the group consisting of 
       
         
           
           
               
               
           
         
       
     
     
         7 . The compound of  claim 6 , selected from the group consisting of compounds identified by ID NOS: B89, B96, B97, B125, B126, and B129. 
     
     
         8 . The compound of  claim 5 , wherein R 1  is 
       
         
           
           
               
               
           
         
       
     
     
         9 . The compound of  claim 5 , wherein R 2  is phenyl substituted with one or more R 17  substituents. 
     
     
         10 . The compound of  claim 5 , where R 2  is 4-phenoxyphenyl and the phenoxy group is substituted with one or more R 17  substituents. 
     
     
         11 . The compound of  claim 5 , wherein R 2  is selected from 
       
         
           
           
               
               
           
         
       
     
     
         12 . The compound of  claim 1 , having the structure IV 
       
         
           
           
               
               
           
         
         wherein, 
         L 1 , L 2  and —N(SO 2 Me)- together with the attached carbons of the aromatic ring to form a 5-12 member ring, containing 1-4 heteroatoms of N, O, S, P and/or Si; 
         L 1  or L 2  is independently selected from the group consisting of a bond, —O—, —C(R 15 R 16 )—, —NR 3 —, —S(O) n —, —P(O)—, —Si(R 4 R 5 )—, —C(O)—, —C(O)O—, and substituted alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycle, aryl, heteroaryl, amide, carbamate, urea, and sulfonamide; 
         n is 0, 1, or 2; and 
         R 2  is an aryl or heteroaryl having one or more R 17  substituents; 
         R 3  is selected from the group of hydrogen, alkylcarbonyl, cycloalkylcarbonyl, alkoxylcarbonyl, cycloalkoxycarbonyl, alkylsulfonyl and cycloalkylsulfonyl; 
         R 4  and R 5  are independently methyl, ethyl, or cyclopropyl; 
         R 15 , R 16  is independently hydrogen, hydroxyl, azide, C 2-4  alkenyl, C 2-4  alkynyl, C 1-4  alkyl, cyclopropyl, C 1-4  alkoxy, or cyclopropoxy or R 15  and R 16  together are a carbonyl or C 1-4  alkenylidene or R 15  and R 16  joined together with the attached carbon are 3-6 member ring optionally containing 0-3 heteroatoms of O, NR N  and/or S; and 
         R 17  is F, Cl or CN 
       
     
     
         13 . The compound of  claim 1 , having the structure II 
       
         
           
           
               
               
           
         
         wherein, 
         L 1 , L 2  and —N(SO 2 Me)- together with the attached carbons of the aromatic ring to form a 5-12 member ring, containing 1-4 heteroatoms of N, O, S, P and/or Si; 
         L 1  or L 2  is independently selected from the group consisting of a bond, —O—, —C(R 15 R 16 )—, —NR 3 —, —S(O) n —, —P(O)—, —Si(R 4 R 5 )—, —C(O)—, —C(O)O—, and substituted alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycle, aryl, heteroaryl, amide, carbamate, urea, and sulfonamide; 
         n is 0, 1, or 2; and 
         R 2  is an aryl or heteroaryl having one or more R 17  substituents; 
         R 3  is selected from the group of hydrogen, alkylcarbonyl, cycloalkylcarbonyl, alkoxylcarbonyl, cycloalkoxycarbonyl, alkylsulfonyl and cycloalkylsulfonyl; 
         R 4  and R 5  are independently methyl, ethyl, or cyclopropyl; 
         R 15 , R 16  is independently hydrogen, hydroxyl, azide, C 2-4  alkenyl, C 2-4  alkynyl, C 1-4  alkyl, cyclopropyl, C 1-4  alkoxy, or cyclopropoxy or R 15  and R 16  together are a carbonyl or C 1-4  alkenylidene or R 15  and R 16  joined together with the attached carbon are 3-6 member ring optionally containing 0-3 heteroatoms of O, NR N  and/or S; 
         R 17  is H, F, Cl or CN; and 
         V is CH, N, CF, CCl, or CCN. 
       
     
     
         14 . The compound of  claim 1 , having the structure: 
       
         
           
           
               
               
           
         
         wherein 
         L 1 , L 2  and —N(SO 2 R 12 )— together with the attached carbons of the aromatic ring to form a 5-12 member ring, containing 1-4 heteroatoms of N, O, S, P and/or Si; 
         L 1  or L 2  is independently selected from the group consisting of a bond, —O—, —C(R 15 R 16 ) NR 3 —, —S(O) n —, —P(O)—, —Si(R 4 R 5 )—, —C(O)—, —C(O)O—, and substituted alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycle, aryl, heteroaryl, amide, carbamate, urea, and sulfonamide; 
         n is 0, 1, or 2; and 
         R 1  is selected from hydrogen, halide, —CF 3 , —CN, —C(O)H, —C(O)OR 6 —, —C(O)NHR 7 , —C(O)N(OH)R 7 , —C(═NOMe)NHR 7 , C(═NOH)NHR 7 , —C(CF 3 )NHR 8 , —C(CN)NHR 9 , —S(O) 2 NHR 10 , —C(═NCN)NHR 11 , 
       
       
         
           
           
               
               
           
         
         R 2  is an aryl or heteroaryl having one or more R 17  substituents; 
         R 3  is selected from the group of hydrogen, alkylcarbonyl, cycloalkylcarbonyl, alkoxylcarbonyl, cycloalkoxycarbonyl, alkylsulfonyl and cycloalkylsulfonyl; 
         R 4  and R 3  are independently methyl, ethyl, or cyclopropyl; 
         R 12  is independently C 1-3  alkyl, cyclopropyl, —OMe, or —NHMe; 
         R 15 , R 16  is independently hydrogen, hydroxyl, azide, C 1-4  alkenyl, C 2-4  alkynyl, C 1-4  alkyl, cyclopropyl, C 1-4  alkoxy, or cyclopropoxy or R 15  and R 16  together are a carbonyl or C 1-4  alkenylidene or R 15  and R 16  joined together with the attached carbon are 3-6 member ring optionally containing 0-3 heteroatoms of O, NR N  and/or S; and 
         R 17  is F, Cl or CN. 
       
     
     
         15 . The compound of  claim 14 , having an inhibitory activity with respect to HCV, as measured by the concentration of the compound effective to produce a half-maximal inhibition of HCV1b replication (EC 50 ) in a 1b_Huh-Luc/Neo-ET cell line in culture, of 100 nM or less. 
     
     
         16 . The compound of  claim 14 , wherein 
       
         
           
           
               
               
           
         
       
       is selected from the group consisting of 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         R 1  is selected from the group consisting of 
       
       
         
           
           
               
               
           
         
       
       and R 2  is selected from the group consisting of 
       
         
           
           
               
               
           
         
       
     
     
         17 . The compound of  claim 16 , selected from the group consisting of compounds identified by ID NOS: B5, B15, B20, B33, B35, B45, B67, B85, B92, B94, B107, B118, B120, B121, B127, B128, B130, B131, B132, B138, B139, B145, B148, B158, B163, B168, B169, B171, B187, B190, B191, B192, B196, B197, B198, B201, B207, B208, B212, B214, B218, B221, B226, B232, B233, B236, B237, B238, B239, B240, B2, B3, B4, B6, B7, B9, B16, B18, B19, B22, B29, B31, B32, B34, B36, B47, B48, B54, B55, B57, B60, B63, B71, B84, B93, B100, B101, B106, B108, B109, B111, B112, B113, B115, B116, B119, B123, B124, B134, B136, B137, B142, B144, B146, B147, B150, B151, B153, B154, B155, B156, B157, B159, B160, B161, B162, B164, B165, B166, B167, B170, B172, B173, B174, B175, B176, B178, B179, B180, B181, B183, B184, B186, B188, B 189, B193, B195, B199, B200, B202, B203, B204, B205, B210, B215, B216, B217, B219, B220, B222, B223, B224, B225, B227, B228, B229, B230, B231, B234, B235, and B241. 
     
     
         18 . The compound of  claim 14 , wherein 
       
         
           
           
               
               
           
         
       
       is selected from the group consisting of 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         19 . The compound of 18, selected from the group consisting of compounds identified by ID NOS: B5, B15, B20, B33, B35, B45, B67, B85, B92, B94, B107, B118, B120, B121, B127, B128, B130, B131, B132, B138, B139, B145, B148, B158, B163, B168, B169, B171, B187, B190, B191, B192, B196, B197, B198, B201, B207, B208, B212, B214, B218, B221, B226, B232, B233, B236, B237, B238, B239, and B240. 
     
     
         20 . The compound of  claim 14 , wherein R 1  is 
       
         
           
           
               
               
           
         
       
     
     
         21 . The compound of  claim 14 , wherein 
       
         
           
           
               
               
           
         
       
       together with the attached carbons of the aromatic ring is a seven- or eight-member ring. 
     
     
         22 . The compound of  claim 14 , wherein R 2  is phenyl substituted with one or more R 17  substituents. 
     
     
         23 . The compound of  claim 14 , where R 2  is 4-phenoxyphenyl and the phenoxy group is substituted with one or more R 17  substituents. 
     
     
         24 . The compound of  claim 14 , wherein R 2  is selected from 
       
         
           
           
               
               
           
         
       
     
     
         25 . The compound of  claim 1 , having the structure VIII 
       
         
           
           
               
               
           
         
         wherein, 
         L 1 , L 2  and —N(SO 2 Me)- together with the attached carbons of the aromatic ring to form a 5-12 member ring, containing 1-4 heteroatoms of N, O, S, P and/or Si; 
         L 1  or L 2  is independently selected from the group consisting of a bond, —O—, —C(R 15 R 16 )—, —NR 3 —, —S(O) n —, —P(O)—, —Si(R 4 R 5 )—, —C(O)—, —C(O)O—, and substituted alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycle, aryl, heteroaryl, amide, carbamate, urea, and sulfonamide; 
         n is 0, 1, or 2; and 
         R 2  is an aryl or heteroaryl having one or more R 17  substituents; 
         R 3  is selected from the group of hydrogen, alkylcarbonyl, cycloalkylcarbonyl, alkoxylcarbonyl, cycloalkoxycarbonyl, alkylsulfonyl and cycloalkylsulfonyl; 
         R 4  and R 5  are independently methyl, ethyl, or cyclopropyl; 
         R 15 , R 16  is independently hydrogen, hydroxyl, azide, C 2-4  alkenyl, C 2-4  alkynyl, C 1-4  alkyl, cyclopropyl, C 1-4  alkoxy, or cyclopropoxy or R 15  and R 16  together are a carbonyl or C 1-4  alkenylidene or R 15  and R 16  joined together with the attached carbon are 3-6 member ring optionally containing 0-3 heteroatoms of O, NR N  and/or S; 
         R 17  is H, F, Cl or CN; and 
         V is CH, N, CF, CCl, or CCN. 
       
     
     
         26 . A pharmaceutical composition containing the compound of  claim 1  together with one or more pharmaceutically acceptable excipients or vehicles, and optionally other therapeutic and/or prophylactic ingredients. 
     
     
         27 . The composition of  claim 26 , containing the compound of  claim 7  or  17 . 
     
     
         28 . The composition of  claim 26 , containing the compound of  claim 19 . 
     
     
         29 . The composition of  claim 26 , formulated for oral delivery. 
     
     
         30 . The composition of  claim 26 , which further includes a second anti-HCV agent selected from the group consisting of interferon-alpha, ribavirin, NS3 protease inhibitors, replicase inhibitors and/or NS5A inhibitors. 
     
     
         31 . A method of treating HCV infection in a subject comprising
 administering to the subject, a pharmaceutically acceptable dose of the compound of  claim 1 , and   continuing said administering until a selected reduction of in the subject's HCV titer is achieved.   
     
     
         32 . The method of  claim 31 , wherein the compound administered is the compound of  claim 7  or  17 . 
     
     
         33 . The method of  claim 31 , wherein the compound administered is the compound of  claim 19 . 
     
     
         34 . The method of  claim 31 , which further includes administering to the subject, either in a single or separate administrations, a second anti-HCV agent selected from the group consisting of interferon-alpha, ribavirin, or both. 
     
     
         35 . The method of  claim 31 , wherein said administering is by oral administration. 
     
     
         36 . The compound of  claim 1 , for use in the treatment of HCV infection in an infected subject. 
     
     
         37 . The compound of  claim 7  or  17  for use in the treatment of HCV infection in an infected subject. 
     
     
         38 . The compound of  claim 19 , for use in the treatment of HCV infection in an infected subject. 
     
     
         39 . The use of the compound of  claim 1  in the preparation of a medicament for the treatment of HCV in an HCV-infected subject. 
     
     
         40 . The use of the compound of  claim 7  or  17  in the preparation of a mediment for the treatment of HCV in an HCV-infected subject. 
     
     
         41 . The use of the compound of  claim 19  in the preparation of a mediment for the treatment of HCV in an HCV-infected subject.

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