US2013331443A1PendingUtilityA1

Multi-arm polymeric prodrug conjugates of taxane-based compounds

Assignee: KOZLOWSKI ANTONIPriority: Dec 22, 2010Filed: Dec 22, 2011Published: Dec 12, 2013
Est. expiryDec 22, 2030(~4.4 yrs left)· nominal 20-yr term from priority
C08G 65/33337C07D 305/14A61K 31/337C08L 2203/02C08G 65/329A61P 35/00A61K 47/60
60
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Claims

Abstract

Among other aspects, provided herein are multi-arm polymeric prodrug conjugates of taxane-based compounds and/or fluorinated forms thereof. Methods of preparing such conjugates as well as methods of administering the conjugates are also provided. Upon administration to a patient, release of the taxane-based compound is achieved.

Claims

exact text as granted — not AI-modified
1 . A conjugate having a structure encompassed by the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 R is a residue of a polyol, polythiol or polyamine bearing from 3 to about 50 hydroxyl, thiol or amino groups; 
 each Q is a linker; 
 each POLY 1  is a water-soluble, non-peptidic polymer; 
 each X is spacer moiety; 
 each R 1  is selected from the group consisting of H, a hydroxy protecting group and 
 
       
         
           
           
               
               
           
         
       
       and each of D 1 , D 2  and D 3  is independently selected from the group consisting of H, F, D and CF 3 ;
 each R 2  is selected from the group consisting of H, a hydroxy protecting group and 
 
       
         
           
           
               
               
           
         
       
       and (a) is either zero or one and each of D 4 , D 5  and D 6  is independently selected from the group consisting of H, F, D and CF 3 ;
 each R 3  is 
 
       
         
           
           
               
               
           
         
       
       and each of D 7 , D 8 , D 9 , D 10 , D 11 , D 12 , D 13 , D 14  and D 15  is independently selected from the group consisting of H, F, D and CF 3 ; and
 q is a positive integer from 3 to about 50, 
 
       and pharmaceutically acceptable salts and solvates thereof, with the proviso that when each R 1  and R 2  are H, R 3  is 
       
         
           
           
               
               
           
         
       
       with at least one of D 7 , D 8 , D 9 , D 10 , D 11 , D 12 , D 13 , D 14  and D 15  is F, D or CF 3 . 
     
     
         2 . The conjugate of  claim 1 , wherein R is a residue of a polyol. 
     
     
         3 . The conjugate of  claim 2 , wherein the polyol is selected from the group consisting of glycerol, diglycerol, triglycerol, hexaglycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol and ethoxylated forms of glycerol. 
     
     
         4 . The conjugate of  claim 3 , wherein the polyol is pentaerythritol. 
     
     
         5 . The conjugate of  claim 1 , wherein the linker is selected from the group consisting of —O—, —S—, —NH—, —NH—C(O)—, and —C(O)—NH—. 
     
     
         6 . The conjugate of  claim 8 , wherein the linker is —O—. 
     
     
         7 . The conjugate of  claim 1 , wherein the water-soluble, non-peptidic polymer is a poly(ethylene oxide). 
     
     
         8 . The conjugate of  claim 1 , wherein the spacer moiety has the structure corresponding to —Y—Z—, where Y is
   —(CR x R y ) a —K w —(CR x R y ) b —(CH 2 CH 2 O) c —(CR x R y ) d —K z —,
 
 
       wherein:
 each R x  and R y , in each occurrence, is independently H or an organic radical selected from the group consisting of alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, and substituted aryl, 
 (a) is zero or an integer of from 1 to 12; 
 (b) is zero or an integer of from 1 to 12; 
 (c) is zero or an integer of from 1 to 25; 
 (d) is zero or an integer of from 1 to 12; 
 K w  is selected from the group consisting of —NH—, —C(O)—, —C(O)NH—, —NH—C(O)—, —O—, —S—, O—C(O)—, C(O)—O—, —O—C(O)—O—, O—C(O)—NH—, —NH—C(O)—O—; and 
 K z  is selected from the group consisting of —NH—, —C(O)—, —C(O)NH—, —NH—C(O)—, —O—, —S—, —O—C(O)—, C(O)—O—, —O—C(O)—O—, —O—C(O)—NH—, —NH—C(O)—O—, and 
 Z is selected from —C(O)—O—, O—C(O)—O—, —O—C(O)—NH— and —NH—C(O)—O—. 
 
     
     
         9 . The conjugate of  claim 1 , wherein the spacer moiety has the structure corresponding to —Y—, where Y is
   —(CR x R y ) a —K w —(CR x R y ) b —(CH 2 CH 2 O) c —(CR x R y ) d —K z —,
 
 
       wherein:
 each R x  and R y , in each occurrence, is independently H or an organic radical selected from the group consisting of alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, and substituted aryl, 
 (a) is zero or an integer of from 1 to 12; 
 (b) is zero or an integer of from 1 to 12; 
 (c) is zero or an integer of from 1 to 25; 
 (d) is zero or an integer of from 1 to 12; 
 K w  is selected from the group consisting of —NH—, —C(O)—, —C(O)NH—, —NH—C(O)—, —O—, —S—, O—C(O)—, C(O)—O—, —O—C(O)—O—, O—C(O)—NH—, —NH—C(O)—O—; and 
 K z  is selected from the group consisting of —NH—, —C(O)—, —C(O)NH—, —NH—C(O)—, —O—, —S—, O—C(O)—, C(O)—O—, —O—C(O)—O—, O—C(O)—NH—, —NH—C(O)—O—. 
 
     
     
         10 . The conjugate of  claim 1 , wherein the spacer moiety has the structure
   —C(O)—(CH 2 ) b —(CH 2 CH 2 O) c —(CH 2 ) d —K z —,
   
       wherein:
 (b) is an integer of from 1 to 5; 
 (c) is an integer of from 1 to 5; 
 (d) is an integer of from 1 to 5; and 
 K z  is selected from the group consisting of —NH—, —C(O)—, —C(O)NH—, —NH—C(O)—, —O—, —S—, —O—C(O)—, C(O)—O—, —O—C(O)—O—, O—C(O)—NH—, —NH—C(O)—O—. 
 
     
     
         11 . The conjugate of  claim 1 , wherein the spacer moiety has the structure —[CH 2 ] m — or —CH 2 —C(O)—NH—C(R 4 )H—, wherein m is a positive integer and R 4  is selected from the group consisting of H, CH 3 , CH(CH 3 ) 2 , CH 2 CH(CH 3 ) 2  and C(H)(CH 3 )CH 2 CH 3 . 
     
     
         12 . The conjugate of  claim 1 , wherein “q” is an integer from 3 to 10. 
     
     
         13 . The conjugate of  claim 1 , wherein each R 1  and R 2  is a hydroxy protecting group. 
     
     
         14 . The conjugate of  claim 1 , wherein each R 1  is 
       
         
           
           
               
               
           
         
       
       and each of D 1 , D 2  and D 3  is independently selected from the group consisting of H, F, D and CF 3 . 
     
     
         15 . The conjugate of  claim 1 , wherein each R 2  is 
       
         
           
           
               
               
           
         
       
       and (a) is either zero or one and each of D 4 , D 5  and D 6  is independently selected from the group consisting of H, F, D and CF 3 . 
     
     
         16 . The conjugate of  claim 15 , wherein (a) is zero. 
     
     
         17 . The conjugate of  claim 1 , wherein R 3  is 
       
         
           
           
               
               
           
         
       
     
     
         18 . The conjugate of  claim 1 , wherein R 3  is 
       
         
           
           
               
               
           
         
       
       and each of D 7 , D 8 , D 9 , D 10 , D 11 , D 12 , D 13 , D 14  and D 15  is independently selected from the group consisting of H, F, D and CF 3 . 
     
     
         19 . The conjugate of  claim 1 , wherein R 3  is 
       
         
           
           
               
               
           
         
       
       and each of D 7 , D 8 , D 9 , D 10 , D 12 , D 13 , D 14  and D 15  is D. 
     
     
         20 . A conjugate having a structure encompassed by the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 each n is a positive integer from 10 to about 400; 
 each R 1  is selected from the group consisting of H, a hydroxy protecting group and 
 
       
         
           
           
               
               
           
         
       
       and each of D 1 , D 2  and D 3  is independently selected from the group consisting of H, F, D and CF 3 ;
 each R 2  is selected from the group consisting of H, a hydroxy protecting group and 
 
       
         
           
           
               
               
           
         
       
       and (a) is either zero or one and each of D 4 , D 5  and D 6  is independently selected from the group consisting of H, F, D and CF 3 ; each R 3  is 
       
         
           
           
               
               
           
         
       
       and each of D 7 , D 8 , D 9 , D 10 , D 11 , D 12 , D 13 , D 14  and D 15  is independently selected from the group consisting of H, F, D and CF 3 ;
 R 4  is selected from the group consisting of H, CH 3 , CH(CH 3 ) 2 , CH 2 CH(CH 3 ) 2  and C(H)(CH 3 )CH 2 CH 3 ; and 
 q is a positive integer from 3 to about 50, 
 
       and pharmaceutically acceptable salts and solvates thereof, with the proviso that when each R 1  and R 2  are H, R 3  is 
       
         
           
           
               
               
           
         
       
       with at least one of D 7 , D 8 , D 9 , D 10 , D 11 , D 12 , D 13 , D 14  and D 15  is F, D or CF 3 . 
     
     
         21 . A conjugate having a structure encompassed by the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 each n is a positive integer from 10 to about 400; 
 each m is a positive integer from 1 to about 12; 
 each R 1  is selected from the group consisting of H, a hydroxy protecting group and 
 
       
         
           
           
               
               
           
         
       
       and each of D 1 , D 2  and D 3  is independently selected from the group consisting of H, F, D and CF 3 ;
 each R 2  is selected from the group consisting of H, a hydroxy protecting group and 
 
       
         
           
           
               
               
           
         
       
       and (a) is either zero or one and each of D 4 , D 5  and D 6  is independently selected from the group consisting of H, F, D and CF 3 ;
 each R 3  is 
 
       
         
           
           
               
               
           
         
       
       and each of D 7 , D 8 , D 9 , D 10 , D 11 , D 12 , D 13 , D 14  and D 15  is independently selected from the group consisting of H, F, D and CF 3 ; and
 q is a positive integer from 3 to about 50, 
 
       and pharmaceutically acceptable salts and solvates thereof, with the proviso that when each R 1  and R 2  are H, R 3  is 
       
         
           
           
               
               
           
         
       
       with at least one of D 7 , D 8 , D 9 , D 10 , D 11 , D 12 , D 13 , D 14  and D 15  is F, D or CF 3 . 
     
     
         22 . A conjugate having a structure encompassed by the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 each n is a positive integer from 10 to about 400; 
 each L 1  is —(CH 2 ) 0-6 C(═O)—; 
 each L 2  is —NH(CH 2 CH 2 O) 1-10 (CHR 5 ) 1-6 —, wherein each R 5  is independently selected from the group consisting of H and lower alkyl; 
 each R 1  is selected from the group consisting of H, a hydroxy protecting group and 
 
       
         
           
           
               
               
           
         
       
       and each of D 1 , D 2  and D 3  is independently selected from the group consisting of H, F, D and CF 3 ;
 each R 2  is selected from the group consisting of H, a hydroxy protecting group and 
 
       
         
           
           
               
               
           
         
       
       and (a) is either zero or one and each of D 4 , D 5  and D 6  is independently selected from the group consisting of H, F, D and CF 3 ;
 each R 3  is 
 
       
         
           
           
               
               
           
         
       
       and each of D 7 , D 8 , D 9 , D 10 , D 11 , D 12 , D 13 , D 14  and D 15  is independently selected from the group consisting of H, F, D and CF 3 ; and
 q is a positive integer from 3 to about 50, 
 
       and pharmaceutically acceptable salts and solvates thereof, with the proviso that when each R 1  and R 2  are H, R 3  is 
       
         
           
           
               
               
           
         
       
       with at least one of D 7 , D 8 , D 9 , D 10 , D 11 , D 12 , D 13 , D 14  and D 15  is F, D or CF 3 . 
     
     
         23 . A conjugate having a structure encompassed by the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 each n is a positive integer from 10 to about 400; 
 each L 1  is —(CH 2 ) 0-6 C(═O)—; 
 each L 3  is —[NH(CHR 5 ) 1-6 C(═O)] 1-4 —, wherein each R 5  is independently selected from the group consisting of H and lower alkyl; 
 each R 1  is selected from the group consisting of H, a hydroxy protecting group and 
 
       
         
           
           
               
               
           
         
       
       and each of D 1 , D 2  and D 3  is independently selected from the group consisting of H, F, D and CF 3 ;
 each R 2  is selected from the group consisting of H, a hydroxy protecting group and 
 
       
         
           
           
               
               
           
         
       
       and (a) is either zero or one and each of D 4 , D 5  and D 6  is independently selected from the group consisting of H, F, D and CF 3 ;
 each R 3  is 
 
       
         
           
           
               
               
           
         
       
       and each of D 7 , D 8 , D 9 , D 10 , D 11 , D 12 , D 13 , D 14  and D 15  is independently selected from the group consisting of H, F, D and CF 3 ; and
 q is a positive integer from 3 to about 50, 
 
       and pharmaceutically acceptable salts and solvates thereof, with the proviso that when each R 1  and R 2  are H, R 3  is 
       
         
           
           
               
               
           
         
       
       with at least one of D 7 , D 8 , D 9 , D 10 , D 11 , D 12 , D 13 , D 14  and D 15  is F, D or CF 3 . 
     
     
         24 . A conjugate having a structure encompassed by the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 each n is a positive integer from 10 to about 400; 
 each L 1  is —C(═O)—; 
 each L 3  is —[NH(CHR 5 ) 1-6 C(═O)] 1-4 —, wherein each R 5  is independently selected from the group consisting of H and lower alkyl; 
 each R 1  is selected from the group consisting of H, a hydroxy protecting group and 
 
       
         
           
           
               
               
           
         
       
       and each of D 1 , D 2  and D 3  is independently selected from the group consisting of H, F, D and CF 3 ;
 each R 2  is selected from the group consisting of H, a hydroxy protecting group and 
 
       
         
           
           
               
               
           
         
       
       and (a) is either zero or one and each of D 4 , D 5  and D 6  is independently selected from the group consisting of H, F, D and CF 3 ;
 each R 3  is 
 
       
         
           
           
               
               
           
         
       
       and each of D 7 , D 8 , D 9 , D 10 , D 11 , D 12 , D 13 , D 14  and D 15  is independently selected from the group consisting of H, F, D and CF 3 ; and
 q is a positive integer from 3 to about 50, 
 
       and pharmaceutically acceptable salts and solvates thereof, with the proviso that when each R 1  and R 2  are H, R 3  is 
       
         
           
           
               
               
           
         
       
       with at least one of D 7 , D 8 , D 9 , D 10 , D 11 , D 12 , D 13 , D 14  and D 15  is F, D or CF 3 . 
     
     
         25 . A conjugate selected from the group consisting of 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein each n is a positive integer from 10 to about 400, and pharmaceutically acceptable salts of each of the foregoing. 
     
     
         26 . A composition comprising a plurality of conjugates, wherein at least 80% of the conjugates in the composition have a structure encompassed by  claim 1 . 
     
     
         27 . The composition of  claim 26 , further comprising a pharmaceutical excipient.

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