US2016024075A1PendingUtilityA1

Indole and benzofuran fused isoquinuclidene derivatives and processes for preparing them

Assignee: DEMERX INCPriority: Jan 25, 2012Filed: Oct 2, 2015Published: Jan 28, 2016
Est. expiryJan 25, 2032(~5.5 yrs left)· nominal 20-yr term from priority
C07D 453/00C07D 471/22C07D 491/22
51
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Claims

Abstract

Provided herein are indole and benzofuran fused isoquinuclidene derivatives. Also provided herein are processes, preferably enantioselective processes, for preparing such derivatives including processes for preparing (−) and (+) noribogaine or a salt thereof, in substantially enantiomerically pure forms.

Claims

exact text as granted — not AI-modified
1 - 10 . (canceled) 
     
     
         11 . A compound of Formula (I)-j or (VI)-j: 
       
         
           
           
               
               
           
         
       
       or a salt or enantiomer thereof wherein
 k is 1, 2, or 3; 
 each R 1  is independently selected from the group consisting of hydrogen, halo, amino, hydroxy, C 1 -C 6  alkoxy, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, cyano, nitro, -N 3 , and -CO 2 H or an ester thereof, wherein the alkyl, alkoxy, alkenyl, or the alkylnyl group is optionally substituted with 1-3 substituents selected from the group consisting of keto, halo, amino, hydroxy, cyano, nitro, —N 3 , phenyl optionally substituted with 1-3 substituents selected from the group consisting of C 1 -C 6  alkyl and C 1 -C 6  alkoxy, and —CO 2 H or an ester thereof; 
 R 2  is hydrogen or C(R 2 ) 2  is a keto group; 
 R 3  is selected from the group consisting of hydrogen, halo, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, wherein the alkyl, alkenyl, or the alkylnyl group is optionally substituted with 1-3 substituents selected from the group consisting of keto, halo, amino, hydroxy, cyano, nitro, —N 3 , and —CO 2 H or an ester thereof; 
 each R 4  independently is selected from the group consisting of hydrogen, hydroxy, —SR 41 , —OR 42 , C 1 -C 6  alkyl, C 2 -C 6  alkenyl, and C 2 -C 6  alkynyl, wherein the alkyl, alkenyl, or the alkynyl group is optionally substituted with 1-3 substituents selected from the group consisting of keto, halo, C 1 -C 6  alkoxy, amino, hydroxy, cyano, nitro, —NHCOCH 3 , —N 3 , and —CO 2 H or an ester thereof, or the 2 R 4  groups together with the carbon atom to which they are bonded to form a keto (C═O) group, a Schiff base (=NR 43 ), a vinylidene moiety of formula =CR 48 R 49 , or form a cyclic ketal or thioketal, which cyclic ketal or thioketal is of formula: 
 
       
         
           
           
               
               
           
         
         each R 41  is independently selected from the group consisting of C 1 -C 6  alkyl optionally substituted with 1-3 substituents selected from the group consisting of C 6 -C 10  aryl, C 3 -C 8  cycloalkyl, C 2 -C 10  heteroaryl, C 3 -C 8  heterocyclyl, halo, amino, —N 3 , hydroxy, C 1 -C 6  alkoxy, silyl, nitro, cyano, and CO 2 H or an ester thereof, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 6 -C 10  aryl, C 2 -C 10  heteroaryl, C 3 -C 8  cycloalkyl, and C 3 -C 8  heterocyclyl; 
         each R 42  is independently selected from the group consisting of C 1 -C 6  alkyl optionally substituted with 1-3 substituents selected from the group consisting of C 6 -C 10  aryl, C 3 -C 8  cycloalkyl, C 2 -C 10  heteroaryl, C 3 -C 8  heterocyclyl, halo, amino, -N 3 , hydroxy, C 1 -C 6  alkoxy, silyl, nitro, cyano, and CO 2 H or an ester thereof, C 2 -C 6  alkenyl, and C 2 -C 6  alkynyl; 
         where X in both occurrences is either oxygen or sulfur; 
         m is 1, 2, 3, or 4; 
         n is 1 or 2; 
         R 43  is selected from the group consisting of C 6 -C 10  aryl and C 2 -C 10  heteroaryl; 
         R 44  is selected from the group consisting of C 1 -C 6  alkyl and C 6 -C 10  aryl; 
         R 48  is hydrogen, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, and C 2 -C 6  alkynyl, wherein the alkyl, alkenyl, or the alkynyl group is optionally substituted with 1-3 substituents selected from the group consisting of keto, C 1 -C 6  alkoxy, amino, hydroxy, cyano, nitro, -NHCOCH 3 , and -CO 2 H or an ester thereof; 
         R 49  is hydrogen or C 1 -C 6  alkyl; and 
         R 51  is selected from the group consisting of hydrogen and C 1 -C 6  alkyl optionally substituted with 1-3 substituents selected from the group consisting of keto, halo, amino, hydroxy, cyano, nitro, —N 3 , and —CO 2 H or an ester thereof; 
         wherein the C 14  content of a compound of Formula (I), that is ibogaine, ibogamine, noribogaine, or methoxy ibogaine is less than 0.9 ppt. 
       
     
     
         12 . The compound of  claim 11 , of Formula (IA): 
       
         
           
           
               
               
           
         
         wherein k and R 1 , R 2 , R 3 , R 4 , and R 51  are defined as in  claim 11 . 
       
     
     
         13 . The compound of  claim 11 , of Formula (IIA): 
       
         
           
           
               
               
           
         
         wherein k and R 1 , R 2 , R 4 , and R 51  are defined as in  claim 11 . 
       
     
     
         14 . The compound of  claim 11 , of Formula (IIIA): 
       
         
           
           
               
               
           
         
         wherein k and R 1 , R 3 , R 4 , and R 51  are defined as in  claim 11 . 
       
     
     
         15 . The compound of  claim 11 , of Formula (IVA): 
       
         
           
           
               
               
           
         
         wherein R 11  is selected from the group consisting of hydrogen and C 1 -C 6  alkyl optionally substituted with 1-3 substituents selected from the group consisting of halo, amino, hydroxy, cyano, nitro, —N 3 , and —CO 2 H or an ester thereof, and phenyl optionally substituted with 1-3 substituents selected from the group consisting of C 1 -C 6  alkyl and C 1 -C 6  alkoxy; 
         k is 1 or 2; 
         and R 1 , R 2 , R 3 , R 4 , and R 51  are defined as in  claim 11 . 
       
     
     
         16 . The compound of  claim 11 , of Formula (IVC) or (VIA): 
       
         
           
           
               
               
           
         
         wherein R 11  is selected from the group consisting of hydrogen and C 1 -C 6  alkyl optionally substituted with 1-3 substituents selected from the group consisting of halo, amino, hydroxy, cyano, nitro, —N 3 , and —CO 2 H or an ester thereof, and phenyl optionally substituted with 1-3 substituents selected from the group consisting of C 1 -C 6  alkyl and C 1 -C 6  alkoxy; 
         k is 1 or 2; 
         and R 1 , R 2 , R 3 , R 4 , and R 51  are defined as in  claim 11 . 
       
     
     
         17 . An isolated enantiomer of a compound of any one of  claims 11 - 16  in substantial enantiomeric excess. 
     
     
         18 . The compound of  claim 11  of Formula (VA): 
       
         
           
           
               
               
           
         
         wherein the substituents are as tabulated below: 
       
       
         
           
                 
                 
                 
                 
                 
                 
               
                     
                 
                   R 1   
                   R 11   
                   C(R 2 ) 2   
                   R 45   
                   R 46   
                   R 47   
                 
                     
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   C═O 
                   CR 45 CR 46  is 
                   — 
                   — 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                   C═O 
                 
                   OH, 4-OMe, 6- 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   C═O 
                   CR 45 CR 46  is 
                   — 
                   — 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                   C═CR 48 H, R 48   
                 
                   OH, 4-OMe, 6- 
                     
                     
                   is Me, Et, Pr, 
                 
                   OMe, or 7-OMe 
                     
                     
                   Bu 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   CH 2   
                   CR 45 CR 46  is 
                   — 
                   — 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                   C═CR 48 H, R 48   
                 
                   OH, 4-OMe, 6- 
                     
                     
                   is Me, Et, Pr, 
                 
                   OMe, or 7-OMe 
                     
                     
                   Bu 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   C═O 
                   CH═CHR 47   
                   OH 
                   H, or C 1 -C 4  alkyl optionally 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   substituted with an OMe group, OH 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   group, an amide, or with an amino 
                 
                   OMe, or 7-OMe 
                     
                     
                     
                     
                   group 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   C═O 
                   C≡CR 47   
                   OH 
                   H or C 1 -C 4  alkyl optionally substituted 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   with an OMe group, OH group, an 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   amide, or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   C═O 
                   CH 2 CH 2 R 47   
                   H 
                   C 1 -C 4  alkyl optionally substituted with 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   an OMe group, OH group, an amide, 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   C═O 
                   CH 2 CH 2 R 47   
                   OH 
                   C 1 -C 4  alkyl optionally substituted with 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   an OMe group, OH group, an amide, 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   CH 2   
                   CH═CHR 47   
                   OH 
                   H or C 1 -C 4  alkyl optionally substituted 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   with an OMe group, OH group, an 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   amide, or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   CH 2   
                   C≡CR 47   
                   OH 
                   H or C 1 -C 4  alkyl optionally substituted 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   with an OMe group, OH group, an 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   amide, or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   CH 2   
                   CH 2 CH 2 R 47   
                   H 
                   C 1 -C 4  alkyl optionally substituted with 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   an OMe group, OH group, an amide, 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   CH 2   
                   CH 2 CH 2 R 47   
                   OH 
                   C 1 -C 4  alkyl optionally substituted with 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   an OMe group, OH group, an amide, 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   H 
                   C═O 
                   CH═CHR 47   
                   OH 
                   H or C 1 -C 4  alkyl optionally substituted 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   with an OMe group, OH group, an 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   amide, or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   H 
                   C═O 
                   C≡CR 47   
                   OH 
                   H or C 1 -C 4  alkyl optionally substituted 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   with an OMe group, OH group, an 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   amide, or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   H 
                   C═O 
                   CH 2 CH 2 R 47   
                   H 
                   C 1 -C 4  alkyl optionally substituted with 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   an OMe group, OH group, an amide, 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   H 
                   C═O 
                   CH 2 CH 2 R 47   
                   OH 
                   C 1 -C 4  alkyl optionally substituted with 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   an OMe group, OH group, an amide, 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   H 
                   CH 2   
                   CH═CHR 47   
                   OH 
                   H or C 1 -C 4  alkyl optionally substituted 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   with an OMe group, OH group, an 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   amide, or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   H 
                   CH 2   
                   C≡CR 47   
                   OH 
                   H or C 1 -C 4  alkyl optionally substituted 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   with an OMe group, OH group, an 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   amide, or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   H 
                   CH 2   
                   CH 2 CH 2 R 47   
                   H 
                   C 1 -C 4  alkyl optionally substituted with 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   an OMe group, OH group, an amide, 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   H 
                   CH 2   
                   CH 2 CH 2 R 47   
                   OH 
                   C 1 -C 4  alkyl optionally substituted with 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                     
                   an OMe group, OH group, an amide, 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                     
                   or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                     
                 
             
                
                
                
               
               
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         19 . The compound of  claim 11  of Formula (VIC): 
       
         
           
           
               
               
           
         
         wherein the substituents are as tabulated below: 
       
       
         
           
                 
                 
                 
                 
                 
               
                     
                 
                   R 1   
                   R 11   
                   C(R 2 ) 2   
                   R 45   
                   R 47   
                 
                     
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   C═O 
                   CH═CHR 47   
                   H or C 1 -C 4  alkyl optionally substituted 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                   with an OMe group, OH group, an 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                   amide, or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   C═O 
                   C≡CR 47   
                   H or C 1 -C 4  alkyl optionally substituted 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                   with an OMe group, OH group, an 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                   amide, or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   C═O 
                   CH 2 CH 2 R 47   
                   C 1 -C 4  alkyl optionally substituted with 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                   an OMe group, OH group, an amide, or 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                   with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   CH 2   
                   CH═CHR 47   
                   H or C 1 -C 4  alkyl optionally substituted 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                   with an OMe group, OH group, an 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                   amide, or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   CH 2   
                   C≡CR 47   
                   H or C 1 -C 4  alkyl optionally substituted 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                   with an OMe group, OH group, an 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                   amide, or with an amino group 
                 
                   OMe, or 7-OMe 
                 
                   H, 4-Me, 6-Me, 7- 
                   Bn 
                   CH 2   
                   CH 2 CH 2 R 47   
                   C 1 -C 4  alkyl optionally substituted with 
                 
                   Me, 4-OH, 6-OH, 7- 
                     
                     
                     
                   an OMe group, OH group, an amide, or 
                 
                   OH, 4-OMe, 6- 
                     
                     
                     
                   with an amino group 
                 
                   OMe, or 7-OMe 
                 
                     
                 
             
                
                
                
               
               
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         20 . The compound of  claim 11 , wherein R 51  is C 1 -C 6  alkyl optionally substituted with 1-3 substituents selected from the group consisting of keto, halo, amino, hydroxy, cyano, nitro, —N 3 , and —CO 2 H or an ester thereof. 
     
     
         21 . The compound of  claim 11 , wherein R 1  is a non-hydrogen substituent, and k is 2. 
     
     
         22 . The compound of  claim 11 , wherein R 1  is a non-hydrogen substituent, and k is 3. 
     
     
         23 . The compound of  claim 18 , wherein R 47  is CH 2 OMe, (CH 2 ) 2 OMe, (CH 2 ) 3 OMe, (CH 2 ) 4 OMe), CH 2 OH, (CH 2 ) 2 0H, (CH 2 ) 3 OH, (CH 2 ) 4 OH), (CH 2 ) 2 NHCOMe, (CH 2 ) 3 NHCOMe, (CH 2 ) 4 NHCCOMe), 
       
         
           
           
               
               
           
         
       
     
     
         24 . The compound of  claim 18 , wherein R 47  is methyl, ethyl, propyl, or butyl each optionally substituted with an OMe group, OH group, an amide, or with an amino group. 
     
     
         25 . The compound of  claim 19 , wherein R 47  is CH 2 OMe, (CH 2 ) 2 OMe, (CH 2 ) 3 OMe, (CH 2 ) 4 OMe), CH 2 OH, (CH 2 ) 2 OH, (CH 2 ) 3 OH, (CH 2 ) 4 OH), (CH 2 ) 2 NHCOMe, (CH 2 ) 3 NHCOMe, (CH 2 ) 4 NHCCOMe), 
       
         
           
           
               
               
           
         
       
     
     
         26 . The compound of  claim 18 , wherein R 47  is methyl, ethyl, propyl, or butyl each optionally substituted with an OMe group, OH group, an amide, or with an amino group.

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