US2017066751A1PendingUtilityA1

Difluorolactam compounds as ep4 receptor-selective agonists for use in the treatment of ep4-mediated diseases and conditions

Assignee: CAYMAN CHEMICAL CO INCPriority: Jul 19, 2012Filed: Sep 16, 2016Published: Mar 9, 2017
Est. expiryJul 19, 2032(~6 yrs left)· nominal 20-yr term from priority
A61P 43/00A61P 25/02A61P 27/02A61P 27/06A61P 29/02A61P 27/00A61P 25/00A61P 19/10A61P 19/08A61P 17/00A61P 17/14A61P 19/00C07D 207/26A61L 27/12A61L 24/0015A61L 24/02A61K 31/4025A61K 9/0053C07D 409/06A61L 2430/02A61L 27/54C07D 207/273A61L 27/3608A61L 24/0042A61L 2300/412A61L 27/58A61L 27/365A61K 31/4015A61L 2300/604A61K 9/0019
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Claims

Abstract

Disclosed herein are compounds of formula (I) and therapeutic methods of treatment with compounds of formula (I), wherein L 1 , L 2 , L 4 , R 1 , R 4 , R 5 , R 6 , and s are as defined in the specification. Compounds of formula (I) are EP4 agonists useful in the treatment of glaucoma, neuropathic pain, and related disorders.

Claims

exact text as granted — not AI-modified
1 - 20 . (canceled) 
     
     
         21 . A compound of formula 
       
         
           
           
               
               
           
         
       
       wherein:
 B is 
 
       
         
           
           
               
               
           
         
       
       L 1  is
 a) C 3 -C 7 alkylene, C 3 -C 7 alkenylene, or C 3 -C 7 alkynylene; or 
 b) (CH 2 ) n -G 2 -(CH 2 ) p , —(CH 2 ) n —C≡C-G 2 -, or —(CH 2 ) n —C(R 13 )═C(R 13 )-G 2 -, wherein n is 1, 2, 3, 4, or 5, p is 0, 1, 2, or 3, and n+p=1, 2, 3, 4, 5, or 6; 
 G 2  is 
 
       
         
           
           
               
               
           
         
         R 10  is H, C 1 -C 4  alkyl, or aryl; 
         R 13 , at each occurrence, is independently H or C 1 -C 4 alkyl; 
         R 4  and R 5  are each independently H or C 1 -C 4  alkyl; or R 4  and R 5  together with the carbon to which they are attached form a C 3 -C 5  cycloalkyl; 
         R 6  is aryl, heteroaryl, C 3 -C 10 alkyl, C 3 -C 10 alkenyl, C 3 -C 10 alkynyl, C 3 -C 10 haloalkyl, C 3 -C 10 haloalkenyl, C 3 -C 10 haloalkynyl, or L 3 -R 7 ; wherein the aryl and heteroaryl are optionally substituted with 1, 2, 3, or 4 substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 3 haloalkyl, cyano, halogen, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy; and -C 1 -C 3 alkylene-C 1 -C 3 alkoxy; 
         L 3  is C 1 -C 6 alkylene, C 2 -C 6 alkenylene, or C 2 -C 6 alkynylene; and 
         R 7  is C 3 -C g cycloalkyl, aryl, heteroaryl, or heterocyclyl; wherein R 7  is optionally substituted with 1, 2, 3, or 4 substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 3 haloalkyl, cyano, halogen, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, and -C 1 -C 3 alkylene-C 1 -C 3 alkoxy. 
       
     
     
         22 . The compound of  claim 21 , wherein:
 L 1  is n-hexylene, (CH 2 ) n -G 2 -(CH 2 ) p , —(CH 2 ) n —C≡C-G 2 -, or —(CH 2 ) n —C(R 13 )═C(R 13 )-G 2 -;   G 2  is   
       
         
           
           
               
               
           
         
         R 4  and R 5  are each independently H or C 1 -C 4  alkyl; 
         R 6  is phenyl, C 3 -C 10 alkyl, C 3 -C 10 alkenyl, C 3 -C 10 alkynyl, C 3 -C 10 haloalkyl, C 3 -C 10 haloalkenyl, C 3 -C 10 haloalkynyl, or L 3 -R 7 ; wherein the phenyl is optionally substituted with 1, 2, 3, or 4 substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 3 haloalkyl, cyano, halogen, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, and -C 1 -C 3 alkylene-C 1 -C 3 alkoxy; and 
         R 7  is phenyl; wherein R 7  is optionally substituted with 1, 2, 3, or 4 substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 3 haloalkyl, cyano, halogen, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, and -C  1 -C 3 alkylene-C  1 -C 3 alkoxy. 
       
     
     
         23 . The compound of  claim 22  wherein:
 L 1  is —(CH 2 ) 3 -G 2 -; 
 R 4  is methyl; 
 R 5  is hydrogen; 
 R 6  is C 3 -C 10 alkynyl or L 3 -R 7 ; 
 L 3  is C 1 -C 6 alkylene; and 
 R 7  is phenyl. 
 
     
     
         24 . The compound of  claim 22  wherein:
 L 1  is (CH 2 ) 3 -G 2 -; 
 R 4  is hydrogen; 
 R 5  is methyl; 
 R 6  is C 3 -C 10 alkynyl or L 3 -R 7 ; 
 L 3  is C 1 -C 6 alkylene; and 
 R 7  is phenyl. 
 
     
     
         25 . A compound of formula 
       
         
           
           
               
               
           
         
       
       wherein:
 L i  is
 a) C 3 -C 7 alkylene, C 3 -C 7 alkenylene, or C 3 -C 7 alkynylene; or 
 b) —(CH 2 ) n -G 2 -(CH 2 ) p , —(CH 2 ) n —C≡C-G 2 -, or —(CH 2 ) n —C(R 13 )═C(R 13 )-G 2 -, wherein n is 1, 2, 3, 4, or 5, p is 0, 1, 2, or 3, and n+p=1, 2, 3, 4, 5, or 6; 
 
 G 2  is 
 
       
         
           
           
               
               
           
         
         R 1  is CO 2 R 10 ; 
         R 10  is H, C 1 -C 4  alkyl, or aryl; and 
         R 13 , at each occurrence, is independently H or C 1 -C 4 alkyl. 
       
     
     
         26 . The compound of  claim 25  wherein:
 L 1  is n-hexylene, —(CH 2 ) n -G 2 -(CH 2 ) p , —(CH 2 ) n —C≡C-G 2 -, or —(CH 2 ) n —C(R 13 )═C(R 13 )-G 2 -; 
 G 2  is 
 
       
         
           
           
               
               
           
         
       
       and
 the oxygen protecting group is 1-ethoxyethyl or tert-butyldimethylsilyl. 
 
     
     
         27 . The compound of  claim 26  wherein
 L 1  is —(CH 2 ) 3 -G 2 -. 
 
     
     
         28 . The compound of  claim 25  of formula 
       
         
           
           
               
               
           
         
       
     
     
         29 . A method of preparing the compound of  claim 28  comprising reacting a compound of formula 
       
         
           
           
               
               
           
         
       
       with a compound of formula LG-L 1 -R 1 , wherein LG is a leaving group and L 1  and R 1  are as defined in  claim 28 . 
     
     
         30 . The method of  claim 29  wherein:
 L 1  is n-hexylene, —(CH 2 ) n -G 2 -(CH 2 ) p , —(CH 2 ) n —C≡C-G 2 -, or —(CH 2 ) n —C(R 13 )═C(R 13 )-G 2 -; 
 G 2  is 
 
       
         
           
           
               
               
           
         
       
       and
 the oxygen protecting group is 1-ethoxyethyl or tert-butyldimethylsilyl. 
 
     
     
         31 . The method of  claim 30  wherein:
 L 1  is —(CH 2 ) 3 -G 2 -; and 
 the oxygen protecting group is tert-butyldimethylsilyl. 
 
     
     
         32 . The method of  claim 29  comprising reacting the compound of formula 
       
         
           
           
               
               
           
         
       
       with the compound of formula LG-L 1 -R 1  and sodium hydride. 
     
     
         33 . The method of  claim 29 , wherein LG is iodo, bromo, chloro, trifluoromethanesulfonyl, methanesulfonyl, toluenesulfonyl, or 4-nitrobenzenesulfonyl. 
     
     
         34 . The method of  claim 33 , wherein LG is bromo. 
     
     
         35 . The method of  claim 32 , wherein LG is iodo, bromo, chloro, trifluoromethanesulfonyl, methanesulfonyl, toluenesulfonyl, or 4-nitrobenzenesulfonyl. 
     
     
         36 . The method of  claim 35 , wherein LG is bromo. 
     
     
         37 . A compound of formula 15 
       
         
           
           
               
               
           
         
       
       wherein:
 B is 
 
       
         
           
           
               
               
           
         
         R 4  and R 5  are each independently H or C 1 -C 4  alkyl; or R 4  and R 5  together with the carbon to which they are attached form a C 3 -0 5  cycloalkyl; 
         R 6  is aryl, heteroaryl, C 3 -C 10 alkenyl, C 3 -C 10 alkynyl, C 3 -C 10 haloalkyl, C 3 -C 10 haloalkenyl, C 3 -C 10 haloalkynyl, or L 3 -R 7 ; wherein the aryl and heteroaryl are optionally substituted with 1, 2, 3, or 4 substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 3 haloalkyl, cyano, halogen, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy; and C 1 -C 3 alkyleneC 1 -C 3 alkoxy; 
         L 3  is C 1 -C 6 alkylene, C 2 -C 6 alkenylene, or C 2 -C 6 alkynylene; and 
         R 7  is C 3 -C g cycloalkyl, aryl, heteroaryl, or heterocyclyl; wherein R 7  is optionally substituted with 1, 2, 3, or 4 substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 3 haloalkyl, cyano, halogen, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, and C 1 -C 3 alkyleneC 1 -C 3 alkoxy. 
       
     
     
         38 . The compound of  claim 37  wherein:
 R 4  and R 5  are each independently H or C 1 -C 4  alkyl; 
 R 6  is phenyl, C 3 -C 10 alkyl, C 3 -C 10 alkenyl, C 3 -C 10 alkynyl, C 3 -C 10 haloalkyl, C 3 -C 10 haloalkenyl, C 3 -C 10 haloalkynyl, or L 3 -R 7 ; wherein the phenyl is optionally substituted with 1, 2, 3, or 4 substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 3 haloalkyl, cyano, halogen, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, and C 1 -C 3 alkyleneC 1 -C 3 alkoxy; and 
 R 7  is phenyl; wherein R 7  is optionally substituted with 1, 2, 3, or 4 substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 3 haloalkyl, cyano, halogen, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, and C  1 -C 3 alkyleneC  1 -C 3 alkoxy. 
 
     
     
         39 . The compound of  claim 38  wherein:
 R 4  is methyl; 
 R 5  is hydrogen; 
 R 6  is C 3 -C 10 alkynyl or L 3 -R 7 ; 
 L 3  is C 1 -C 6 alkylene; and 
 R 7  is phenyl. 
 
     
     
         40 . The compound of  claim 39  wherein:
 R 4  is hydrogen; 
 R 5  is methyl; 
 R 6  is C 3 -C 10 alkynyl or L 3 -R 7 ; 
 L 3  is C 1 -C 6 alkylene; and 
 R 7  is phenyl.

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