US2009264346A1PendingUtilityA1

Macrocyclic peptides active against the hepatitis c virus

60
Assignee: BOEHRINGER INGELHEIM INTPriority: Jan 21, 2004Filed: Jun 29, 2009Published: Oct 22, 2009
Est. expiryJan 21, 2024(expired)· nominal 20-yr term from priority
A61P 31/12A61P 31/00A61P 31/20A61P 31/14A61P 43/00C07K 5/0827A61K 38/00C07K 5/0812C07K 5/0808
60
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Claims

Abstract

Compounds of formula (I): wherein R 1 , R 2 , X, R 3 , D, and the dotted line b are as defined herein; or a pharmaceutically acceptable salt or ester thereof, are useful as inhibitors of the HCV NS3 protease.

Claims

exact text as granted — not AI-modified
1 . A compound of formula (I): 
     
       
         
         
             
             
         
       
       wherein R 1  is hydroxy; 
       R 2  is a group of formula: 
     
     
       
         
         
             
             
         
       
       wherein
 R 20  is H, OH, halogen, or Y 1 —R 20a  wherein Y 1  is a bond, O, S, or NR 20b  and wherein:
 R 20a  is selected from the group consisting of: (C 1-8 )alkyl, (C 1-6 )alkyl-C≡N, (C 2-8 )alkenyl, (C 2-8 )alkynyl and (C 3-7 )cycloalkyl, each of said alkyl, alkenyl, alkynyl and cycloalkyl being optionally substituted with one, two or three substituents, each independently selected from:
 halogen, (C 1-6 )alkyl optionally substituted with —O—(C 1-6 )alkyl or —O—(C 3-6 )cycloalkyl, (C 3-7 )cycloalkyl, —O—(C 1-6 )alkyl, Het, —O—(C 3-6 )cycloalkyl, —NH 2 , —NH(C 1-4 )alkyl and —N((C 1-4 )alkyl) 2 ; and 
 
 R 20b  is H, (C 1-6 )alkyl or (C 3-6 )cycloalkyl; 
 and W is N; and the dotted line “a” is a double bond; or 
 
 R 20  is oxo, and W is NR 23  wherein R 23  is H, (C 1-6 )alkyl, (C 2-6 )alkenyl or (C 2-6 )alkynyl; and the dotted line “a” is a single bond; 
 R 21  is halogen or Y 2 —R 21a , wherein Y 2  is a bond, O, S, SO or SO 2 , and R 21a  is (C 1-6 )alkyl, (C 2-6 )alkenyl, (C 2-6 )alkynyl, (C 3-7 )cycloalkyl or (C 3-7 )cycloalkyl-(C 1-6 )alkyl-; 
 R 22  is H, —OH, —O—(C 1-4 )alkyl, —NH 2 , —NH(C 1-4 )alkyl or —N((C 1-4 )alkyl) 2 ; 
 
       or R 2  is a group of formula: 
     
     
       
         
         
             
             
         
       
       wherein
 R 20 , W and the dotted line “a” are as defined above; 
 R 24  is H or R 21  as defined above; and 
 R 25  is H or (C 1-6 )alkyl; 
 
       X is O or NH; 
       R 3  is (C 1-10 )alkyl, (C 3-7 )cycloalkyl or (C 3-7 )cycloalkyl-(C 1-4 )alkyl-,
 a) wherein the cycloalkyl and cycloalkyl-alkyl- may be mono-, di- or tri-substituted with (C 1-3 )alkyl; 
 b) wherein the alkyl, cycloalkyl and cycloalkyl-alkyl- may be mono- or di-substituted with substituents each independently selected from hydroxy and O—(C 1-6 )alkyl; 
 c) wherein each alkyl group may be mono-, di- or tri-substituted with halogen; and 
 d) wherein in each cycloalkyl group being 5-, 6- or 7-membered, one or two —CH 2 -groups not being directly linked to each other may be replaced by —O— such that the O-atom is linked to the group X via at least two C-atoms; 
 
       D is a 3 to 8 atom saturated or unsaturated alkylene chain; and 
       the dotted line “b” is a single bond or a double bond; 
       wherein Het as used herein is defined as a 3- to 7-membered heterocycle having 1 to 4 heteroatoms each independently selected from O, N and S, which may be saturated, unsaturated or aromatic, and which is optionally fused to at least one other cycle to form a 4- to 14-membered heteropolycycle having wherever possible 1 to 5 heteroatoms, each independently selected from O, N and S, said heteropolycycle being saturated, unsaturated or aromatic; 
       or a pharmaceutically acceptable salt or ester thereof. 
     
   
   
       2 . The compound according to  claim 1  wherein R 2  is a group of formula: 
     
       
         
         
             
             
         
       
       wherein 
       W, R 20 , R 21 , R 22  and the dotted line “a” are defined as in  claim 1 . 
     
   
   
       3 . The compound according to  claim 2  wherein R 20  is oxo; W is NR 23  wherein R 23  is Me, Et, —CH 2 CH═CH 2  or H; and the dotted line “a” is a single bond. 
   
   
       4 . The compound according to  claim 2  wherein W is N; the dotted line “a” is a double bond; and R 20  is H, OH, halogen, or Y 1 —R 20a  wherein
 Y 1  is a bond, O, S, or NR 20b ;   R 20a  is selected from the group consisting of: (C 1-8 )alkyl, (C 2-8 )alkenyl, (C 2-8 )alkynyl and (C 3-7 )cycloalkyl, each of said alkyl, alkenyl, alkynyl and cycloalkyl being optionally substituted with one, two or three substituents, each independently selected from:
 halogen, (C 1-6 )alkyl, (C 3-7 )cycloalkyl, Het, —O—(C 1-6 )alkyl, —O—(C 3-6 )cycloalkyl, —NH 2 , —NH(C 1-4 )alkyl and —N((C 1-4 )alkyl) 2 ; and 
   R 20b  is H, (C 1-6 )alkyl or (C 3-6 )cycloalkyl.   
   
   
       5 . The compound according to  claim 2  wherein W is N; the dotted line “a” is a double bond; and R 20  is H, (C 1-6 )alkyl, OH, —O—(C 1-6 )alkyl, —S—(C 1-6 )alkyl, —(CH 2 ) 0-4 —CH═CH 2 , —(CH 2 ) 0-4 —C≡CH, —O—(CH 2 ) 0-4 —CH═CH 2 , —O—(CH 2 ) 0-4 —C≡CH, —O—(CH 2 ) 1-4 —OMe; —O—(CH 2 ) 1-4 —N(Me) 2 ; —O—(CH 2 ) 1-4 -Het; —S—(CH 2 ) 0-4 —CH═CH 2 , —S—(CH 2 ) 0-4 —C≡CH, —S—(CH 2 ) 1-4 —OMe; —S—(CH 2 ) 1-4 —N(Me) 2 , —S—(CH 2 ) 1-4 -Het; (C 3-6 )cycloalkyl, —O—(C 3-6 )cycloalkyl, O—(C 1-6 )alkyl-(C 3-6 )cycloalkyl, —S—(C 3-6 )cycloalkyl, or —S—(C 1-6 )alkyl-(C 3-6 )cycloalkyl; wherein Het is 5- or 6-membered monocyclic heteroaryl containing from one to three heteroatoms each independently selected from N, O and S;
 each of said (C 1-6 )alkyl, —O—(C 1-6 )alkyl, —S—(C 1-6 )alkyl, —(CH 2 ) 0-4 —CH═CH 2 , —(CH 2 ) 0-4 —C≡CH, —O—(CH 2 ) 0-4 —CH═CH 2 , —O—(CH 2 ) 0-4 —C≡CH, —S—(CH 2 ) 0-4 —CH═CH 2 , —S—(CH 2 ) 0-4 —C≡CH, (C 3-6 )cycloalkyl, —O—(C 3-6 )cycloalkyl, and —S—(C 3-6 )cycloalkyl being optionally substituted with one, two or three substituents, each independently selected from (C 1-4 )alkyl, —O—(C 1-4 )alkyl, and halo;   or R 20  is NR 20a R 20b  wherein R 20a  is (C 1-4 )alkyl, and R 20b  is H, (C 1-4 )alkyl or (C 3-5 )cycloalkyl.   
   
   
       6 . The compound according to  claim 5  wherein R 20  is H, methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, —CH═CH 2 , —C≡CH, O-methyl, O-ethyl, O-propyl, O—CH(CH 3 ) 2 , 0-cyclopropyl, O-cyclobutyl, O-cyclopentyl, O-cyclohexyl, O—CH 2 CH 2 CF 3 , —O—CH═CH 2 , —O—CH 2 —CH═CH 2 , O—C≡CH, —O—CH 2 —C≡CH, —O—CH 2 —C≡CCH 3 , —O—CH 2 —CH 2 —OMe, —O—CH 2 —CH 2 —N(Me) 2 ,S-methyl, S-ethyl, S-propyl, S—CH(CH 3 ) 2 , S-cyclopropyl, S-cyclobutyl, S-cyclopentyl, S-cyclohexyl, —S—CH═CH 2 , —S—CH 2 —CH═CH 2 , S—C≡CH, —S—CH 2 —C≡CH, —S—CH 2 —CH 2 —OMe, —S—CH 2 —CH 2 —N(Me) 2 , 
     
       
         
         
             
             
         
       
     
   
   
       7 . The compound according to  claim 2  wherein R 21  is selected from: fluorine, chlorine, bromine, —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —OCH 3 , —OCH 2 CH 3 , —OCH 2 CH 2 CH 3 , —SCH 3 , —SCH 2 CH 3 , —SCH 2 CH 2 CH 3 , —(SO)CH 3 , —(SO)CH 2 CH 3 , —(SO)CH 2 CH 2 CH 3 , —(SO 2 )CH 3 , —(SO 2 )CH 2 CH 3 , —(SO 2 )CH 2 CH 2 CH 3 , 
     
       
         
         
             
             
         
       
     
     and —C≡CH. 
   
   
       8 . The compound according to  claim 2  wherein R 22  is selected from: H, —OH, —OCH 3 , —OCH 2 CH 3 , —OCH 2 CH 2 CH 3 , —NHCH 3 , —N(CH 3 ) 2 , —N(CH 3 )CH 2 CH 3  and —N(CH 3 )CH 2 CH 2 CH 3 . 
   
   
       9 . The compound according to  claim 8  wherein R 22  is H or —OCH 3 . 
   
   
       10 . The compound according to  claim 1  wherein R 2  is a group of formula: 
     
       
         
         
             
             
         
       
       wherein 
       W, R 20 , R 24 , R 25  and the dotted line “a” are defined as in  claim 1 . 
     
   
   
       11 . The compound according to  claim 10  wherein W is N; the dotted line “a” is a double bond; and R 20  is H, OH, halogen, or Y 1 —R 20a  wherein
 Y 1  is a bond, O, S, or NR 20b ;   R 20a  is selected from the group consisting of: (C 1-8 )alkyl, (C 2-8 )alkenyl, (C 2-8 )alkynyl and (C 3-7 )cycloalkyl, each of said alkyl, alkenyl, alkynyl and cycloalkyl being optionally substituted with one, two or three substituents, each independently selected from:
 halogen, (C 1-6 )alkyl, (C 3-7 )cycloalkyl, Het, —O—(C 1-6 )alkyl, —O—(C 3-6 )cycloalkyl, —NH 2 , —NH(C 1-4 )alkyl and —N((C 1-4 )alkyl) 2 ; and 
   R 20b  is H, (C 1-6 )alkyl or (C 3-6 )cycloalkyl.   
   
   
       12 . The compound according to  claim 11  wherein R 20  is Y 1 —R 20a , wherein Y 1  is 0 and R 20a  is (C 1-8 )alkyl. 
   
   
       13 . The compound according to  claim 10  wherein R 24  is H or (C 1-6 )alkyl. 
   
   
       14 . The compound according to  claim 10  wherein R 25  is H. 
   
   
       15 . The compound according to  claim 1  wherein X is O. 
   
   
       16 . The compound according to  claim 1  wherein R 3  is selected from (C 2-8 )alkyl, (C 3-7 )cycloalkyl and (C 3-7 )cycloalkyl-(C 1-3 )alkyl-,
 a) wherein said cycloalkyl and cycloalkyl-alkyl- may be mono-, di- or tri-substituted with (C 1-3 )alkyl; and   b) wherein said alkyl, cycloalkyl and cycloalkyl-alkyl- may be mono- or di-substituted with substituents each independently selected from hydroxy and O—(C 1-4 )alkyl; and   c) wherein each of said alkyl groups may be mono-, di- or tri-substituted with fluorine or mono-substituted with chlorine or bromine; and   d) wherein in each of said cycloalkyl groups being 5-, 6- or 7-membered, one or two —CH 2 -groups not being directly linked to each other may be replaced by —O— such that the O-atom is linked to the group X via at least two C-atoms.   
   
   
       17 . The compound according to  claim 16  wherein R 3  is selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and a group selected from: 
     
       
         
         
             
             
         
       
     
   
   
       18 . The compound according to  claim 1  wherein linker D is a 5 carbon atom chain. 
   
   
       19 . The compound according to  claim 1  wherein the dotted line “b” is a single bond or a double bond in the Z (cis) configuration. 
   
   
       20 . The compound according to  claim 1  of formula (Ia): 
     
       
         
         
             
             
         
       
       wherein R 1  is hydroxy; 
       R 20  is H, OH, halogen, or Y 1 —R 20a  wherein Y 1  is a bond, O, S, or NR 20b  wherein:
 R 20a  is selected from the group consisting of: (C 1-8 )alkyl, (C 1-6 )alkyl-C≡N, (C 2-8 )alkenyl, (C 2-8 )alkynyl, all of said alkyl, alkenyl and alkynyl being optionally mono- or di-substituted with:
 halogen, (C 1-6 )alkyl, —O—(C 1-6 )alkyl, (C 1-4 )alkyl-O—(C 1-6 )alkyl, —O—(C 3-6 )cycloalkyl, (C 1-4 )alkyl-O—(C 3-6 )cycloalkyl, amino, (C 1-4 )alkylamino, or di((C 1-4 )alkyl)amino; and 
 
 R 20b  is H, (C 1-6 )alkyl or (C 3-6 )cycloalkyl; 
 
       and W is N; and the dotted line “a” is a double bond; or 
       R 20  is oxo, and W is NR 23  wherein R 23  is H, (C 1-6 )alkyl, (C 2-6 )alkenyl, (C 2-6 )alkynyl; and the dotted line “a” is a single bond; 
       R 21  is halogen, (C 1-6 )alkyl, (C 2-6 )alkenyl, (C 2-6 )alkynyl, —O—(C 1-6 )alkyl, —O—(C 2-6 )alkenyl, —O—(C 2-6 )alkynyl, —S—(C 1-6 )alkyl, —S—(C 2-6 )alkenyl, and —S—(C 2-6 )alkynyl, wherein the sulfur is in any oxidized state; 
       R 22  is H, —OH, —O—(C 1-4 )alkyl, —NH 2 , —NH(C 1-4 )alkyl or —N((C 1-4 )alkyl) 2 ; 
       X is O or NH; 
       R 3  is (C 1-10 )alkyl, (C 3-7 )cycloalkyl, (C 3-7 )cycloalkyl-(C 1-4 )alkyl-,
 a) wherein the cycloalkyl and cycloalkyl-alkyl- may be mono-, di- or tri-substituted with (C 1-3 )alkyl; 
 b) wherein the alkyl, cycloalkyl and cycloalkyl-alkyl- may be mono- or di-substituted with substituents selected from hydroxy and O—(C 1-6 )alkyl; 
 c) wherein all the alkyl groups may be mono-, di- or tri-substituted with halogen; and 
 d) wherein in the cycloalkyl groups, being 5-, 6- or 7-membered, one or two —CH 2 -groups not being directly linked to each other may be replaced by —O—; 
 
       D is a 3 to 8 atom saturated or unsaturated alkylene chain; and 
       the dotted line “b” is a single bond or a double bond; 
       or a pharmaceutically acceptable salt or ester thereof. 
     
   
   
       21 . The compound according to  claim 1  wherein R 1  is hydroxy;
 R 2  is a group of formula   
     
       
         
         
             
             
         
       
       wherein
 R 20  is oxo, W is NR 23  wherein R 23  is Me, Et, —CH 2 CH═CH 2  or H and the dotted line “a” is a single bond; or 
 W is N, the dotted line “a” is a double bond; and R 20  is H, OH, halogen, or 
 Y 1 —R 20a  wherein 
 Y 1  is a bond, O, S, or NR 20b ; 
 R 20a  is selected from the group consisting of: (C 1-8 )alkyl, (C 2-8 )alkenyl, (C 2-8 )alkynyl and (C 3-7 )cycloalkyl, each of said alkyl, alkenyl, alkynyl and cycloalkyl being optionally substituted with one, two or three substituents, each independently selected from:
 halogen, (C 1-6 )alkyl, (C 3-7 )cycloalkyl, Het, —O—(C 1-6 )alkyl, —O—(C 3-6 )cycloalkyl, —NH 2 , —NH(C 1-4 )alkyl and —N((C 1-4 )alkyl) 2 ; wherein Het is defined as in  claim 1 ; and 
 R 20b  is H, (C 1-6 )alkyl or (C 3-6 )cycloalkyl; and 
 
 R 21  is selected from: fluorine, chlorine, bromine, —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —OCH 3 , —OCH 2 CH 3 , —OCH 2 CH 2 CH 3 , —SCH 3 , —SCH 2 CH 3 , —SCH 2 CH 2 CH 3 , —(SO)CH 3 , —(SO)CH 2 CH 3 , —(SO)CH 2 CH 2 CH 3 , —(SO 2 )CH 3 , —(SO 2 )CH 2 CH 3 , —(SO 2 )CH 2 CH 2 CH 3 , 
 
     
     
       
         
         
             
             
         
       
     
     and —C≡CH; and
 R 22  is selected from: H, —OH, —OCH 3 , —OCH 2 CH 3 , —OCH 2 CH 2 CH 3 , —NHCH 3 , —N(CH 3 ) 2 , —N(CH 3 )CH 2 CH 3  and —N(CH 3 )CH 2 CH 2 CH 3 ; 
 or R 2  is a group of formula 
 
     
       
         
         
             
             
         
       
       wherein
 W is N; the dotted line “a” is a double bond; and R 20  is H, OH, halogen, or 
 Y 1 —R 20a  wherein
 Y 1  is a bond, O, S, or NR 20b ; 
 R 20a  is selected from the group consisting of: (C 1-8 )alkyl, (C 2-8 )alkenyl, (C 2-8 )alkynyl and (C 3-7 )cycloalkyl, each of said alkyl, alkenyl, alkynyl and cycloalkyl being optionally substituted with one, two or three substituents, each independently selected from:
 halogen, (C 1-6 )alkyl, (C 3-7 )cycloalkyl, Het, —O—(C 1-6 )alkyl, —O—(C 3-6 )cycloalkyl, —NH 2 , —NH(C 1-4 )alkyl and —N((C 1-4 )alkyl) 2 ; wherein Het is defined as in  claim 1 ; and 
 
 R 20b  is H, (C 1-6 )alkyl or (C 3-6 )cycloalkyl; and 
 
 R 24  is H or (C 1-6 )alkyl; and 
 R 25  is H; and 
 
       X is O or NH; and 
       R 3  is selected from (C 2-8 )alkyl, (C 3-7 )cycloalkyl and (C 3-7 )cycloalkyl-(C 1-3 )alkyl-,
 a) wherein said cycloalkyl and cycloalkyl-alkyl- may be mono-, di- or tri-substituted with (C 1-3 )alkyl; and 
 b) wherein said alkyl, cycloalkyl and cycloalkyl-alkyl- may be mono- or di-substituted with substituents each independently selected from hydroxy and O—(C 1-4 )alkyl; and 
 c) wherein each of said alkyl groups may be mono-, di- or tri-substituted with fluorine or mono-substituted with chlorine or bromine; and 
 d) wherein in each of said cycloalkyl groups being 5-, 6- or 7-membered, one or two —CH 2 -groups not being directly linked to each other may be replaced by —O— such that the O-atom is linked to the group X via at least two C-atoms; and 
 
       linker D is a 3 to 8 atom saturated or unsaturated alkylene chain; and 
       the dotted line “b” is a single bond or a double bond. 
     
   
   
       22 . The compound according to  claim 1  wherein
 R 1  is hydroxy;   R 2  is a group of formula   
     
       
         
         
             
             
         
       
       wherein
 R 20  is oxo, W is NR 23  wherein R 23  is Me, Et, —CH 2 CH═CH 2  or H and the dotted line “a” is a single bond; or 
 W is N, the dotted line “a” is a double bond, and R 20  is H, (C 1-6 )alkyl, OH, —O—(C 1-6 )alkyl, —S—(C 1-6 )alkyl, —(CH 2 ) 0-4 —CH═CH 2 , —(CH 2 ) 0-4 —C≡CH, —O—(CH 2 ) 0-4 —CH═CH 2 , —O—(CH 2 ) 0-4 —C≡CH, —O—(CH 2 ) 1-4 —OMe; —O—(CH 2 ) 1-4 —N(Me) 2 ; —O—(CH 2 ) 1-4 -Het; —S—(CH 2 ) 0-4 —CH═CH 2 , —S—(CH 2 ) 0-4 —C≡CH, —S—(CH 2 ) 1-4 —OMe; —S—(CH 2 ) 1-4 —N(Me) 2 , —S—(CH 2 ) 1-4 -Het; (C 3-6 )cycloalkyl, —O—(C 3-6 )cycloalkyl, O—(C 1-6 )alkyl-(C 3-6 )cycloalkyl, —S—(C 3-6 )cycloalkyl, or —S—(C 1-6 )alkyl-(C 3-6 )cycloalkyl; wherein Het is 5- or 6-membered monocyclic heteroaryl containing from one to three heteroatoms each independently selected from N, O and S;
 each of said (C 1-6 )alkyl, —O—(C 1-6 )alkyl, —S—(C 1-6 )alkyl, —(CH 2 ) 0-4 —CH═CH 2 , —(CH 2 ) 0-4 —C≡CH, —O—(CH 2 ) 0-4 —CH═CH 2 , —O—(CH 2 ) 0-4 —C≡CH, —S—(CH 2 ) 0-4 —CH═CH 2 , —S—(CH 2 ) 0-4 —C≡CH, (C 3-6 )cycloalkyl, —O—(C 3-6 )cycloalkyl, and —S—(C 3-6 )cycloalkyl being optionally substituted with one, two or three substituents, each independently selected from (C 1-4 )alkyl, —O—(C 1-4 )alkyl, and halo; 
 or R 20  is NR 20a R 20b  wherein R 20a  is (C 1-4 )alkyl, and R 20 b is H, (C 1-4 )alkyl or (C 3-5 )cycloalkyl; and 
 
 R 21  is selected from: fluorine, chlorine, bromine, —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —OCH 3 , —OCH 2 CH 3 , —OCH 2 CH 2 CH 3 , —SCH 3 , —SCH 2 CH 3 , —SCH 2 CH 2 CH 3 , —(SO)CH 3 , —(SO)CH 2 CH 3 , —(SO)CH 2 CH 2 CH 3 , —(SO 2 )CH 3 , —(SO 2 )CH 2 CH 3 , —(SO 2 )CH 2 CH 2 CH 3 , 
 
     
     
       
         
         
             
             
         
       
       
          and —C≡CH; and 
         R 22  is selected from H, —OCH 3  and —N(CH 3 ) 2 ; 
       
       or R 2  is a group of formula 
     
     
       
         
         
             
             
         
       
       wherein
 W is N; the dotted line “a” is a double bond; 
 R 20  is Y 1 —R 20a , wherein Y 1  is O and R 20a  is (C 1-8 )alkyl; 
 R 24  is H or (C 1-6 )alkyl; and 
 R 25  is H; and 
 
       X is O or NH; and 
       R 3  is selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and a group selected from: 
     
     
       
         
         
             
             
         
       
       and 
       linker D is a 3 to 8 atom saturated or unsaturated alkylene chain; and 
       the dotted line “b” is a single bond or a double bond. 
     
   
   
       23 . The compound according to  claim 1  wherein
 R 1  is hydroxy;   R 2  is a group of formula   
     
       
         
         
             
             
         
       
       wherein
 R 20  is oxo, W is NR 23  wherein R 23  is Me, Et, —CH 2 CH═CH 2  or H and the dotted line “a” is a single bond; or 
 W is N, the dotted line “a” is a double bond, and R 20  is H, methyl, ethyl, 1-methylethyl, —C≡CH, O-methyl, O-ethyl, O— propyl, O—CH(CH 3 ) 2 , O-cyclopentyl, O—CH 2 CH 2 CF 3 , —O—CH═CH 2 , —O—CH 2 —CH═CH 2 , —O—CH 2 —C≡CH, —O—CH 2 —C≡CCH 3 , —O—CH 2 CH 2 OMe, —O—CH 9 CH 9 N(Me) 2 , S-methyl, S-ethyl, S-propyl, S—CH(CH 3 ) 2 , 
 
     
     
       
         
         
             
             
         
       
       
         and 
         R 21  is selected from fluorine, chlorine, bromine, —CH 3 , —OCH 3 , —SCH 3 , —SCH 2 CH 3 , (SO)CH 3 , (SO 2 )CH 3 , —(SO 2 )CH 2 CH 3 , 
       
     
     
       
         
         
             
             
         
       
       
          and —C≡CH; and 
         R 22  is H or —OCH 3 ; 
       
       or R 2  is a group of formula 
     
     
       
         
         
             
             
         
       
       wherein
 W is N; the dotted line “a” is a double bond; 
 R 20  is —O—CH 2 CH 3 ; 
 R 24  is H or CH 3 ; and 
 R 25  is H; and 
 
       X is O; and 
       R 3  is selected from cyclopentyl, 
     
     
       
         
         
             
             
         
       
       and 
       linker D is a 5 carbon atom chain; and 
       the dotted line “b” is a single bond or a double bond in the Z (cis) configuration. 
     
   
   
       24 . The compound according to  claim 1  of the formula: 
     
       
         
         
             
             
         
       
       wherein R 1 , R 20 , R 21  and R 22  are defined as in the table below: 
     
     
       
         
               
               
               
               
               
             
                   
               
                 Cpd 
                 R 22   
                 R 21   
                 R 20   
                 R 1   
               
                   
               
                 101 
                 OMe 
                 Br 
                 OEt 
                 OH 
               
                 102 
                 OMe 
                 Me 
                 OEt 
                 OH 
               
                 103 
                 H 
                 Br 
                 OEt 
                 OH 
               
                 104 
                 H 
                 Cl 
                 OEt 
                 OH 
               
                 105 
                 H 
                 Br 
                 OMe 
                 OH 
               
                 106 
                 H 
                 Cl 
                 OMe 
                 OH 
               
                 107 
                 H 
                 F 
                 OMe 
                 OH 
               
                 108 
                 OMe 
                 Me 
                 OMe 
                 OH 
               
                 109 
                 OMe 
                 Me 
                 H 
                 OH 
               
                 110 
                 H 
                 Cl 
                 H 
                 OH 
               
                 111 
                 H 
                 Br 
                 H 
                 OH 
               
                 112 
                 H 
                 Cl 
                 Me 
                 OH 
               
                 113 
                 H 
                 F 
                 OEt 
                 OH 
               
                 114 
                 H 
                 Me 
                 OEt 
                 OH 
               
                 115 
                 H 
                 Br 
                 Me 
                 OH 
               
                 116 
                 H 
                 Cl 
                 Et 
                 OH 
               
                 117 
                 H 
                 Cl 
                 —CH(CH 3 ) 2   
                 OH 
               
                 118 
                 H 
                 SMe 
                 OEt 
                 OH 
               
                 119 
                 H 
                 Me 
                 O—CH(CH 3 ) 2   
                 OH 
               
                 120 
                 OMe 
                 Me 
                 O—CH(CH 3 ) 2   
                 OH 
               
                 121 
                 H 
                 Cl 
                 O—CH(CH 3 ) 2   
                 OH 
               
                 122 
                 H 
                 Br 
                 O—CH(CH 3 ) 2   
                 OH 
               
                 123 
                 H 
                 F 
                 O—CH(CH 3 ) 2   
                 OH 
               
                 124 
                 H 
                 SO 2 ME 
                 OEt 
                 OH 
               
                 125 
                 H 
                 Cl 
                 SMe 
                 OH 
               
                 126 
                 OMe 
                 Br 
                 OMe 
                 OH 
               
                 127 
                 H 
                 SMe 
                 H 
                 OH 
               
                 128 
                 H 
                 SOMe 
                 H 
                 OH 
               
                 129 
                 H 
                 SO 2 Me 
                 H 
                 OH 
               
                 130 
                 H 
                 Cl 
                 SEt 
                 OH 
               
                 131 
                 H 
                 Cl 
                 OCH 2 CH(CH 3 ) 2   
                 OH 
               
                 132 
                 H 
                 Cl 
                 OCH 2 CH 2 CH 3   
                 OH 
               
                 133 
                 H 
                 OMe 
                 OEt 
                 OH 
               
                 134 
                 H 
                 —C≡CH 
                 OEt 
                 OH 
               
                 137 
                 H 
                 Cl 
                 SCH 2 CH 2 CH 3   
                 OH 
               
                 138 
                 H 
                 Cl 
                 SCH(CH 3 ) 2   
                 OH 
               
                 139 
                 H 
                 Cl 
                 OCH 2 C(CH 3 ) 3   
                 OH 
               
                 140 
                 H 
                 Cl 
                 OCH 2 CH 2 CF 3   
                 OH 
               
                   
               
                 141 
                 H 
                 Cl 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 OH 
               
                   
               
                 142 
                 H 
                 Cl 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 OH 
               
                   
               
                 143 
                 H 
                 Cl 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 OH 
               
                   
               
                 144 
                 H 
                 Cl 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 OH 
               
                   
               
                 145 
                 H 
                 Cl 
                 —C≡CH 
                 OH 
               
                 146 
                 OMe 
                 Br 
                 —OCH 2 C≡CH 
                 OH 
               
                 147 
                 OMe 
                 Br 
                 —OCH 2 CH═CH 2   
                 OH 
               
                   
               
                 148 
                 H 
                 Cl 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 OH 
               
                   
               
                 149 
                 OMe 
                 CH 3   
                 —OCH 2 CH═CH 2   
                 OH 
               
                   
               
                 150 
                 OMe 
                 CH 3   
                 —OCH 2 C≡CH 
                 OH 
               
                 151 
                 OMe 
                 Cl 
                 —OEt 
                 OH 
               
                 152 
                 OMe 
                 Cl 
                 —O—CH(CH 3 ) 2   
                 OH 
               
                 153 
                 OMe 
                 Cl 
                 —OMe 
                 OH 
               
                 154 
                 OMe 
                 Cl 
                 —OCH 2 CH≡CH 2   
                 OH 
               
                 155 
                 OMe 
                 Cl 
                 —OCH 2 C≡CH 
                 OH 
               
                 156 
                 OMe 
                 Br 
                 —OCH 2 C≡CCH 3   
                 OH 
               
                   
               
                 157 
                 H 
                 Cl 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 OH 
               
                   
               
                 158 
                 H 
                 Cl 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 OH 
               
                   
               
                 159 
                 H 
                 Cl 
                 —OCH═CH 2   
                 OH 
               
                   
               
                 160 
                 OMe 
                 Br 
                 —O—CH(CH 3 ) 2   
                 OH 
               
                 161 
                 H 
                 —SEt 
                 —OEt 
                 OH 
               
                 162 
                 H 
                 —SO 2 Et 
                 —OEt 
                 OH 
               
                   
               
                 163 
                 H 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 —OEt 
                 OH 
               
                   
               
           
              
              
              
             
             
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
             
          
         
       
     
   
   
       25 . The compound according to  claim 1  of the formula: 
     
       
         
         
             
             
         
       
       wherein R 1 , R 20 , R 21 , R 22  and R 3  are defined as in the table below: 
     
     
       
         
               
               
               
               
               
               
             
                   
               
                 Cpd 
                 R 3   
                 R 22   
                 R 21   
                 R 20   
                 R 1   
               
                   
               
                 201 
                 Et 
                 H 
                 F 
                 OEt 
                 OH 
               
                   
               
                 202 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
                 F 
                 OEt 
                 OH 
               
                   
               
                 203 
                 —CH 2 CH 2 CH 3   
                 H 
                 F 
                 OEt 
                 OH 
               
                   
               
                 204 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
                 F 
                 OEt 
                 OH 
               
                   
               
                 205 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
                 F 
                 OEt 
                 OH 
               
                   
               
                 206 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
                 Cl 
                 OEt 
                 OH 
               
                   
               
                 207 
                 —CH 2 CH 2 CH 3   
                 H 
                 Cl 
                 OEt 
                 OH 
               
                   
               
                 208 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
                 Cl 
                 OEt 
                 OH 
               
                   
               
                 209 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
                 Cl 
                 OEt 
                 OH 
               
                   
               
                 210 
                 Et 
                 H 
                 Me 
                 OEt 
                 OH 
               
                   
               
                 211 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
                 Me 
                 OEt 
                 OH 
               
                   
               
                 212 
                 —CH 2 CH 2 CH 3   
                 H 
                 Me 
                 OEt 
                 OH 
               
                   
               
                 213 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
                 Me 
                 OEt 
                 OH 
               
                   
               
                 214 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
                 Me 
                 OEt 
                 OH 
               
                   
               
                 215 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
                 Cl 
                 OEt 
                 OH 
               
                   
               
                 216 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
                 Me 
                 OEt 
                 OH 
               
                   
               
           
              
              
              
             
             
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
              
             
          
         
       
     
   
   
       26 . The compound according to  claim 1  of the formula: 
     
       
         
         
             
             
         
       
       wherein R 1 , R 20 , R 21  and R 22  are defined as in the table below: 
     
     
       
         
               
               
               
               
               
             
                   
               
                 Cpd 
                 R 22   
                 R 21   
                 R 20   
                 R 1   
               
                   
               
                 301 
                 OMe 
                 Br 
                 OEt 
                 OH 
               
                 302 
                 H 
                 Br 
                 OEt 
                 OH 
               
                 303 
                 H 
                 Cl 
                 OEt 
                 OH 
               
                 304 
                 H 
                 F 
                 OEt 
                 OH 
               
                 305 
                 OMe 
                 Me 
                 OEt 
                 OH 
               
                 306 
                 H 
                 Me 
                 OEt 
                 OH 
               
                 307 
                 H 
                 F 
                 OMe 
                 OH 
               
                 308 
                 OMe 
                 Me 
                 OMe 
                 OH 
               
                 309 
                 H 
                 Cl 
                 SEt 
                 OH 
               
                   
               
           
              
              
              
             
             
              
              
              
              
              
              
              
              
              
              
             
          
         
       
     
   
   
       27 . The compound according to  claim 1  of the formula: 
     
       
         
         
             
             
         
       
       wherein R 21 , R 22  and R 23  are defined as in the table below: 
     
     
       
         
               
               
               
               
             
                   
               
                 Cpd 
                 R 22   
                 R 21   
                 R 23   
               
                   
               
                 401 
                 OMe 
                 Br 
                 H 
               
                 402 
                 OMe 
                 Br 
                 Me 
               
                 403 
                 OMe 
                 Br 
                 Et 
               
                 404 
                 OMe 
                 Cl 
                 Me 
               
                 405 
                 OMe 
                 Cl 
                 —CH 2 CH═CH 2   
               
                 406 
                 OMe 
                 CH 3   
                 H 
               
                   
               
           
              
              
              
             
             
              
              
              
              
              
              
              
             
          
         
       
     
   
   
       28 . The compound according to  claim 1  of the formula: 
     
       
         
         
             
             
         
       
       wherein R 24  is defined as in the table below: 
     
     
       
         
               
               
               
             
                   
                   
               
                   
                 Cpd 
                 R 24   
               
                   
                   
               
                   
                 501 
                 H 
               
                   
                 502 
                 CH 3   
               
                   
                   
               
           
              
              
              
             
             
              
              
              
             
          
         
       
     
   
   
       29 . A pharmaceutical composition comprising an anti-hepatitis C virally effective amount of a compound according to  claim 1  or a pharmaceutically acceptable salt or ester thereof, and a pharmaceutically acceptable carrier medium or auxiliary agent. 
   
   
       30 . The pharmaceutical composition according to  claim 29  further comprising a therapeutically effective amount of at least one other antiviral agent. 
   
   
       31 . The pharmaceutical composition according to  claim 30 , wherein said antiviral agent is ribavirin. 
   
   
       32 . The pharmaceutical composition according to  claim 30 , wherein said antiviral agent is selected from an other anti-HCV agent, HIV inhibitor, HAV inhibitor and HBV inhibitor. 
   
   
       33 . The pharmaceutical composition according to  claim 32 , wherein said other anti-HCV agent is selected from the group consisting of immunomodulatory agents, other inhibitors of HCV NS3 protease, inhibitors of HCV polymerase and inhibitors of another target in the HCV life cycle. 
   
   
       34 . The pharmaceutical composition according to  claim 33 , wherein said immunomodulatory agent is selected from α-interferon, γ-interferon and pegylated α-interferon. 
   
   
       35 . The pharmaceutical composition according to  claim 33 , wherein said inhibitor of another target in the HCV life cycle is selected from inhibitors of: helicase, NS2/3 protease and internal ribosome entry site (IRES). 
   
   
       36 . A method for the treatment or prevention of a hepatitis C viral infection in a mammal comprising administering to the mammal an anti-hepatitis C virally effective amount of a compound according to  claim 1 , or a pharmaceutically acceptable salt or ester thereof. 
   
   
       37 . A method for the treatment or prevention of a hepatitis C viral infection in a mammal comprising administering to the mammal an anti-hepatitis C virally effective amount of a combination of a compound according to  claim 1 , or a pharmaceutically acceptable salt or ester thereof, and at least one other antiviral agent. 
   
   
       38 . The method according to  claim 37 , wherein said antiviral agent is ribavirin. 
   
   
       39 . The method according to  claim 37  wherein said other antiviral agent is selected from another anti-HCV agent, HIV inhibitor, HAV inhibitor and HBV inhibitor. 
   
   
       40 . The method according to  claim 39 , wherein said other anti-HCV agent is selected from immunomodulatory agents, other inhibitors of HCV NS3 protease, inhibitors of HCV polymerase and inhibitors of another target in the HCV life cycle. 
   
   
       41 . The method according to  claim 40 , wherein said immunomodulatory agent is selected from α-interferon, γ-interferon and pegylated α-interferon. 
   
   
       42 . The method according to  claim 40 , wherein said inhibitor of another target in the HCV life cycle is selected from inhibitors of: helicase, NS2/3 protease and internal ribosome entry site (IRES). 
   
   
       43 . A method of inhibiting the replication of hepatitis C virus by exposing the virus to a hepatitis C viral NS3 protease inhibiting amount of a compound according to  claim 1 , or a pharmaceutically acceptable salt or ester thereof. 
   
   
       44 . An article of manufacture comprising a composition effective to treat an HCV infection or to inhibit the NS3 protease of HCV and packaging material comprising a label which indicates that the composition can be used to treat infection by the hepatitis C virus, wherein said composition comprises a compound according to  claim 1  or a pharmaceutically acceptable salt or ester thereof.

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