US2010234422A1PendingUtilityA1

Sulfonylated Heterocycles Useful for Modulation of the Progesterone Receptor

Assignee: WYETH LLCPriority: Mar 6, 2007Filed: May 26, 2010Published: Sep 16, 2010
Est. expiryMar 6, 2027(~0.6 yrs left)· nominal 20-yr term from priority
A61P 3/04A61P 35/00A61P 43/00A61P 5/24A61P 25/22A61P 25/00C07D 401/04C07D 403/04A61P 15/02A61P 15/08A61P 15/00A61P 1/00A61P 15/18
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Claims

Abstract

Compounds of the following structure are provided, wherein n, R 1 -R 3 and R 6 -R 9 are defined below, as are methods of preparing and using these compounds for contraception; treating or preventing fibroids, uterine leiomyomata, endometriosis, dysfunctional bleeding, polycystic ovary syndrome, and hormone-dependent carcinomas; providing hormone replacement therapy; stimulating food intake; synchronizing estrus; and treating cycle-related symptoms.

Claims

exact text as granted — not AI-modified
1 . A compound of the structure: 
       
         
           
           
               
               
           
         
         wherein:
 n is 2 or 3; 
 Z is CR 4 R 5 , NR 4 , or O; 
 R 1  is selected from the group consisting of C 1  to C 6  alkyl, C 3  to C 8  cycloalkyl, substituted C 1  to C 6  alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycle, substituted heterocycle, C 3  to C 6  alkenyl, substituted C 3  to C 6  alkenyl, C 3  to C 6  alkynyl, and substituted C 3  to C 6  alkynyl; 
 R 2 , R 3 , R 4 , and R 5  are independently selected from the group consisting of H, halogen, CN, C 1  to C 6  alkyl, substituted C 1  to C 6  alkyl, —(CH m X r ) z CH p X q , C 3  to C 6  cycloalkyl, O—C 1  to C 6  alkyl, substituted O—C 1  to C 6  alkyl, O—(CH m X r ) z CH p X q , aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycle, and substituted heterocycle; or 
 R 2  and R 4 ; or R 2  and R 5 ; or R 3  and R 4 ; or R 3  and R 5  are joined to form a carbocyclic or heterocyclic ring containing from 3 to 8 atoms; 
 R 6 , R 7  and R 8  are independently selected from the group consisting of H, halogen, CN, C 1  to C 6  alkyl, substituted C 1  to C 6  alkyl, —(CH m X r ) z CH p X q , C 3  to C 6  cycloalkyl, O—C 1  to C 6  alkyl, substituted O—C 1  to C 6  alkyl, O—(CH m X r ) z CH p X q , aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycle, and substituted heterocycle; 
 X is halogen; 
 m and r are, independently, 0 to 2, provided that m+r=2; 
 p and q are, independently, 0 to 3, provided that p+q=3; 
 z is 0 to 10; and 
 R 9  is selected from the group consisting of H, C 1  to C 6  alkyl, C(O)O—C 1  to C 6  alkyl, C 2  to C 6  alkenyl, C 2  to C 6  alkynyl, substituted C 1  to C 6  alkyl, C 3  to C 6  cycloalkyl, and substituted C 3  to C 6  cycloalkyl; 
 
         or a pharmaceutically acceptable salt, prodrug, tautomer, or metabolite thereof. 
       
     
     
         2 . The compound according to  claim 1 , wherein R 1  is C 1  to C 6  alkyl. 
     
     
         3 . The compound according to  claim 1 , wherein R 2 , R 3 , R 6 , or R 8  is H. 
     
     
         4 . The compound according to  claim 1 , wherein n is 2. 
     
     
         5 . The compound according to  claim 1 , wherein Z is CR 4 R 5 . 
     
     
         6 . The compound according to  claim 1 , wherein R 4  or R 5  is H or C 1  to C 6  alkyl. 
     
     
         7 . The compound according to  claim 1 , wherein R 7  is H or halogen. 
     
     
         8 . The compound according to  claim 1 , wherein R 9  is C 1  to C 6  alkyl. 
     
     
         9 . The compound according to  claim 1 , wherein:
 R 1  is C 1  to C 6  alkyl;   R 2 , R 3 , R 6 , and R 8  are H;   R 4  and R 5  are, independently, H or C 1  to C 6  alkyl;   R 7  is H or halogen; and   R 9  is C 1  to C 6  alkyl.   
     
     
         10 . The compound according to  claim 1 , selected from the group consisting of 1-methyl-5-[1-(methylsulfonyl)-1,2,3,4-tetrahydroquinolin-6-yl]-1H-pyrrole-2-carbonitrile; 5-[1-(ethylsulfonyl)-1,2,3,4-tetrahydroquinolin-6-yl]-1-methyl-1H-pyrrole-2-carbonitrile; and 1-methyl-5-[1-(propylsulfonyl)-1,2,3,4-tetrahydroquinolin-6-yl]-1H-pyrrole-2-carbonitrile; or a pharmaceutically acceptable salt, prodrug, tautomer, or metabolite thereof. 
     
     
         11 . A method of contraception, treating or preventing fibroids, uterine leiomyomata, endometriosis, dysfunctional bleeding, polycystic ovary syndrome, or hormone-dependent carcinomas, providing hormone replacement therapy, stimulating food intake, synchronizing estrus, or treating cycle-related symptoms, said method comprising administering to a mammal in need thereof a compound of  claim 1 . 
     
     
         12 . A method for preparing a compound of formula I: 
       
         
           
           
               
               
           
         
         wherein:
 n is 2 or 3; 
 Z is CR 4 R 5 , NR 4 , or O; 
 R 1  is selected from the group consisting of C 1  to C 6  alkyl, C 3  to C 8  cycloalkyl, substituted C 1  to C 6  alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycle, substituted heterocycle, C 3  to C 6  alkenyl, substituted C 3  to C 6  alkenyl, C 3  to C 6  alkynyl, and substituted C 3  to C 6  alkynyl; 
 R 2 , R 3 , R 4 , and R 5  are independently selected from the group consisting of H, halogen, CN, C 1  to C 6  alkyl, substituted C 1  to C 6  alkyl, —(CH m X r ) z CH p X q , C 3  to C 6  cycloalkyl, O—C 1  to C 6  alkyl, substituted O—C 1  to C 6  alkyl, O—(CH m X r ) z CH p X q , aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycle, and substituted heterocycle; or 
 R 2  and R 4 ; or R 2  and R 5 ; or R 3  and R 4 ; or R 3  and R 5  are joined to form a carbocyclic or heterocyclic ring containing from 3 to 8 atoms; 
 R 6 , R 7  and R 8  are independently selected from the group consisting of H, halogen, CN, C 1  to C 6  alkyl, substituted C 1  to C 6  alkyl, —(CH m X r ) z CH p X q , C 3  to C 6  cycloalkyl, O—C 1  to C 6  alkyl, substituted O—C 1  to C 6  alkyl, O—(CH m X r ) z CH p X q , aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycle, and substituted heterocycle; 
 X is halogen; 
 m and r are, independently, 0 to 2, provided that m+r=2; 
 p and q are, independently, 0 to 3, provided that p+q=3; 
 z is 0 to 10; and 
 R 9  is selected from the group consisting of H, C 1  to C 6  alkyl, C(O)O—C 1  to C 6  alkyl, C 2  to C 6  alkenyl, C 2  to C 6  alkynyl, substituted C 1  to C 6  alkyl, C 3  to C 6  cycloalkyl, and substituted C 3  to C 6  cycloalkyl; 
 
         or a pharmaceutically acceptable salt, prodrug, tautomer, or metabolite thereof;
 said method comprising:
 (a) reacting a cyanopyrrole boronic acid or a tin derivative thereof and a substituted heterocycle of the structure: 
 
 
       
       
         
           
           
               
               
           
         
         
           
             
               wherein, LG is a leaving group; 
             
             (b) sulfonylating the product of step (a). 
           
         
       
     
     
         13 . The method according to  claim 12 , wherein the product of step (a) is of the structure: 
       
         
           
           
               
               
           
         
       
     
     
         14 . The method according to  claim 12 , wherein said boronic acid is of the structure: 
       
         
           
           
               
               
           
         
       
     
     
         15 . A method for preparing a compound of the structure: 
       
         
           
           
               
               
           
         
         wherein:
 n is 2 or 3; 
 Z is CR 4 R 5 , NR 4 , or O; 
 R 1  is selected from the group consisting of C 1  to C 6  alkyl, C 3  to C 5  cycloalkyl, substituted C 1  to C 6  alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycle, substituted heterocycle, C 3  to C 6  alkenyl, substituted C 3  to C 6  alkenyl, C 3  to C 6  alkynyl, and substituted C 3  to C 6  alkynyl; 
 R 2 , R 3 , R 4 , and R 5  are independently selected from the group consisting of H, halogen, CN, C 1  to C 6  alkyl, substituted C 1  to C 6  alkyl, —(CH m X r ) z CH p X q , C 3  to C 6  cycloalkyl, O—C 1  to C 6  alkyl, substituted O—C 1  to C 6  alkyl, O—(CH m X r ) z CH p X q , aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycle, and substituted heterocycle; or 
 R 2  and R 4 ; or R 2  and R 5 ; or R 3  and R 4 ; or R 3  and R 5  are joined to form a carbocyclic or heterocyclic ring containing from 3 to 8 atoms; 
 R 6 , R 7  and R 8  are independently selected from the group consisting of H, halogen, CN, C 1  to C 6  alkyl, substituted C 1  to C 6  alkyl, —(CH m X r ) z CH p X q , C 3  to C 6  cycloalkyl, O—C 1  to C 6  alkyl, substituted O—C 1  to C 6  alkyl, O—(CH m X r ) z CH p X q , aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycle, and substituted heterocycle; 
 X is halogen; 
 m and r are, independently, 0 to 2, provided that m+r=2; 
 p and q are, independently, 0 to 3, provided that p+q=3; 
 z is 0 to 10; and 
 R 9  is selected from the group consisting of H, C 1  to C 6  alkyl, C(O)O—C 1  to C 6  alkyl, C 2  to C 6  alkenyl, C 2  to C 6  alkynyl, substituted C 1  to C 6  alkyl, C 3  to C 6  cycloalkyl, and substituted C 3  to C 6  cycloalkyl; 
 
         or a pharmaceutically acceptable salt, prodrug, tautomer, or metabolite thereof;
 said method comprising:
 (a) sulfonylating a compound of the structure: 
 
 
       
       
         
           
           
               
               
           
         
         
           
             (b) coupling the product of step (a) with a cyanopyrrole boronic acid or a tin derivative thereof. 
           
         
       
     
     
         16 . The method according to  claim 15 , wherein the product of step (a) is of the structure: 
       
         
           
           
               
               
           
         
       
     
     
         17 . A method for preparing a compound of the structure: 
       
         
           
           
               
               
           
         
         wherein:
 n is 2 or 3; 
 Z is CR 4 R 5 , NR 4 , or O; 
 R 1  is selected from the group consisting of C 1  to C 6  alkyl, C 3  to C 8  cycloalkyl, substituted C 1  to C 6  alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycle, substituted heterocycle, C 3  to C 6  alkenyl, substituted C 3  to C 6  alkenyl, C 3  to C 6  alkynyl, and substituted C 3  to C 6  alkynyl; 
 R 2 , R 3 , R 4 , and R 5  are independently selected from the group consisting of H, halogen, CN, C 1  to C 6  alkyl, substituted C 1  to C 6  alkyl, —(CH m X r ) z CH p X q , C 3  to C 6  cycloalkyl, O—C 1  to C 6  alkyl, substituted O—C 1  to C 6  alkyl, O—(CH m X r ) z CH p X q , aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycle, and substituted heterocycle; or 
 R 2  and R 4 ; or R 2  and R 5 ; or R 3  and R 4 ; or R 3  and R 5  are joined to form a carbocyclic or heterocyclic ring containing from 3 to 8 atoms; 
 R 6 , R 7  and R 8  are independently selected from the group consisting of H, halogen, CN, C 1  to C 6  alkyl, substituted C 1  to C 6  alkyl, —(CH m X r ) z CH p X q , C 3  to C 6  cycloalkyl, O—C 1  to C 6  alkyl, substituted O—C 1  to C 6  alkyl, O—(CH m X r ) z CH p X q , aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycle, and substituted heterocycle; 
 X is halogen; 
 m and r are, independently, 0 to 2, provided that m+r=2; 
 p and q are, independently, 0 to 3, provided that p+q=3; 
 z is 0 to 10; and 
 R 9  is selected from the group consisting of H, C 1  to C 6  alkyl, C(O)O—C 1  to C 6  alkyl, C 2  to C 6  alkenyl, C 2  to C 6  alkynyl, substituted C 1  to C 6  alkyl, C 3  to C 6  cycloalkyl, and substituted C 3  to C 6  cycloalkyl; 
 
         or a pharmaceutically acceptable salt, prodrug, tautomer, or metabolite thereof;
 said method comprising:
 (a) sulfonylating a compound of the structure: 
 
 
       
       
         
           
           
               
               
           
         
         
           
             (b) brominating the product of step (a); and 
             (c) coupling the product of step (b) with a cyanopyrrole boronic acid or a tin derivative thereof. 
           
         
       
     
     
         18 . The method according to  claim 17 , wherein the product of step (a) is of the structure: 
       
         
           
           
               
               
           
         
       
     
     
         19 . The method according to  claim 17 , wherein the product of step (b) is of the structure and LG is bromine:

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