Triazole linked carbohydrates

Abstract

Disclosed is an invention concerning triazolyloligosaccharides, oligosaccharides wherein the bonding between the saccharide groups is via a triazole group and methods for their preparation.

1 . A compound having the structure I,  
       
         
           
           
               
               
           
         
         wherein each R, independently, is selected from the group consisting of hydrogen, hydroxy, alkoxy having up to 8 carbon atoms, acyloxy having up to 8 carbon atoms, acylamino having up to 8 carbon atoms, C 1  to C 20  hydrocarbyl and substituted hydrocarbyl and amino;  
         R 3  is selected from the group consisting of H, C 1  to C 20  hydrocarbyl and substituted hydrocarbyl;  
         m is 0 or 1, and  
         n and n′ are, independently, 4 or 5.  
       
     
     
         2 . A compound of the structure II,  
       wherein R 1  is selected from the group consisting of H, Na, C 1 -C 20  alkyl,  
       wherein R 2  is selected from the group consisting of hydroxy, alkoxy having from 1 to 8 carbon atoms, acyloxy having from 1 to 8 carbon atoms, acylamino having  
       
         
           
           
               
               
           
         
       
       from 1 to 8 carbon atoms, amino, hydrogen, and guanidino; 
 wherein R 3  is selected from the group consisting of H, C 1  to C 20  hydrocarbyl, and substituted hydrocarbyl;  
 wherein R 4  is selected from the group consisting of H, acyl having from 1 to 8 carbon atoms, and alkyl having 1 to 20 carbon atoms;  
 wherein R 6  and R 6′  are selected from the group consisting of H, OH, C 1  to C 20  alkoxy, C 1  to C 20  substituted alkoxy, mono-, di- or oligosaccharide, and alkylideneoxy taken together with R 7′  when R 7′  is not H, provided that one of R 6  and R 6′  must be H but R 6  and R 6′  may not both be H; and  
 R 7  and R 7′  are selected from the group consisting of H, acyl having from 1 to 8 carbon atoms, C 1  to C 20  alkyl, aryl, and alkylidene taken together with an adjacent R 6 , R 6′ , R 7  or R 7′ .  
 
     
     
         3 . A compound of the structure III,  
       wherein R 3  is selected from the group consisting of H, C 1  to C 20  hydrocarbyl, and C 1  to C 20  substituted hydrocarbyl; R 8  is selected from the group consisting of H, alkyl having from 1 to 20 carbon atoms, and acyl having from 1 to 8 carbon atoms;  
       
         
           
           
               
               
           
         
       
       wherein R 6  and R 6′  are selected from the group consisting of H, OH, C 1  to C 20  alkoxy, C 1  to C 20  substituted alkoxy, mono-, di- or oligosaccharide, and alkylideneoxy taken together with R 7′ , when R 7′  is not H, provided that one of R 6  and R 6′  must be H but R 6  and R 6′  may not both be H; and 
 wherein R 7  and R 7′  are selected from the group consisting of H, acyl having from 1 to 8 carbon atoms, C 1  to C 20  alkyl, aryl, and alkylidene taken together with an adjacent R 6 , R 6′ , R 7  or R 7′ .  
 
     
     
         4 . A compound of  claim 1  according to structure IV  
       
         
           
           
               
               
           
         
         wherein m=0 and R 3  is H,  
         wherein each R, independently, is selected from the group consisting of hydrogen, hydroxy, alkoxy having up to 8 carbon atoms, acyloxy having up to 8 carbon atoms, acylamino having up to 8 carbon atoms, C 1  to C 20  hydrocarbyl, C 1  to C 20  substituted hydrocarbyl and amino; and  
         n and n′, independently, are 4 or 5.  
       
     
     
         5 . A compound of  claim 2  according to structure V,  
       
         
           
           
               
               
           
         
         wherein R 1  is selected from the group consisting of H, Na, and C 1 -C 20  alkyl,  
         R 2  is selected from the group consisting of hydroxy, alkoxy having from 1 to 8 carbon atoms, acyloxy having from 1 to 8 carbon atoms, acylamino having from 1 to 8 carbon atoms, amino, hydrogen, and guanidino;  
         wherein R 3  of the triazolyl ring is H and the other R 3  is selected from the group consisting of H, C 1  to C 20  hydrocarbyl, and C 1  to C 20  substituted hydrocarbyl;  
         R 4  is selected from the group consisting of H, acyl having from 1 to 8 carbon atoms, and alkyl having from 1 to 20 carbon atoms;  
         R 6  and R 6′  are selected from the group consisting of H, OH, C 1  to C 20  alkoxy, C 1  to C 20  substituted alkoxy, mono-, di- or oligosaccharide, and alkylideneoxy taken together with R 7′ , when R 7′  is not H, provided that one of R 6  and R 6′  must be H but R 6  and R 6′  may not both be H; and  
         R 7  and R 7′  are selected from the group consisting of H, acyl having from 1 to 8 carbon atoms, C 1  to C 20  alkyl, aryl, and alkylidene taken together with an adjacent R 6 , R 6′ , R 7  or R 7′ .  
       
     
     
         6 . The compound according to  claim 3  of the structure VI,  
       
         
           
           
               
               
           
         
         wherein R 8  is selected from selected from the group consisting of H, alkyl having from 1 to 20 carbon atoms, and acyl having from 1 to 8 carbon atoms;  
         R 6  and R 6′  are selected from the group consisting of H, OH, C 1  to C 20  alkoxy, C 1  to C 20  substituted alkoxy, mono-, di- or oligosaccharide, and alkylideneoxy taken together with R 7′  when R 7′  is not H, provided that one of R 6  and R 6′  must be H but R 6  and R 6′  may not both be H; and  
         R 7  and R 7′  are selected from the group consisting of H, acyl having from 1 to 8 carbon atoms, C 1  to C 20  alkyl, aryl, and alkylidene taken together with an adjacent R 6 , R 6′ , R 7  or R 7′ .  
       
     
     
         7 . A process for the preparation of a compound having the structure I, comprising: contacting azides of the structure IA:  
       
         
           
           
               
               
           
         
         wherein R is selected from the group consisting of hydrogen, hydroxy, alkoxy having up to 8 carbon atoms, acyloxy having up to 8 carbon atoms, acylamino having up to 8 carbon atoms, C 1  to C 20  hydrocarbyl or substituted hydrocarbyl and amino; n and n′ are, independently, 4 or 5, and m is 0 or 1, with compounds of the structure IB  
         
           
             
             
                 
                 
             
           
         
         wherein R is as described above and R 3  is selected from the group consisting of H, C 1  to C 20  hydrocarbyl and substituted hydrocarbyl.  
       
     
     
         8 . A process according to  claim 7  for the preparation of triazolyldisaccharides of the structure II, comprising contacting compounds of the structure IIA:  
       
         
           
           
               
               
           
         
         wherein R 1  is selected from the group consisting of H, Na, and C 1 -C 20  alkyl,  
         R 2  is selected from the group consisting of hydroxy, alkoxy having from 1 to 8 carbon atoms, acyloxy having from 1 to 8 carbon atoms, acylamino having from 1 to 8 carbon atoms, amino, hydrogen, and guanidino;  
         R 3  is selected from the group consisting of H, C 1  to C 20  hydrocarbyl and substituted hydrocarbyl; and  
         R 4  is selected from the group consisting of H, acyl having from 1 to 8 carbon atoms and alkyl having 1 to 20 carbon atoms; with compounds of the structure IIB  
         
           
             
             
                 
                 
             
           
         
         wherein R 3  is selected from the group consisting of H, C 1  to C 20  hydrocarbyl and substituted hydrocarbyl;  
         R 6  and R 6′  are selected from the group consisting of H, OH, C 1  to C 20  alkoxy and substituted alkoxy, mono-, di- or oligosaccharide, and alkylideneoxy taken together with R 7′  when R 7′  is not H, provided that one of R 6  and R 6′  must be H but R 6  and R 6  may not both be H; and  
         R 7  and R 7′  are selected from the group consisting of H, acyl having from 1 to 8 carbon atoms, C 1  to C 20  alkyl, aryl, and alkylidene taken together with an adjacent R 6 , R 6′ , R 7  or R 7′ .  
       
     
     
         9 . A process according to  claim 7  for the preparation of a compound of the structure III, comprising: contacting a compound of the structure IIIA:  
       
         
           
           
               
               
           
         
         wherein R 8  is selected from the group consisting of H, alkyl, wherein the alkyl having from 1 to 20 carbon atoms, and acyl, where the acyl group contains from 1 to 8 carbon atoms;  
         with compounds of the structure IIB,  
         
           
             
             
                 
                 
             
           
         
         wherein R 3  is selected from the group consisting of H C 1  to C 20  hydrocarbyl and substituted hydrocarbyl;  
         R 6  and R 6′  are selected from the group consisting of H, OH, C 1  to C 20  alkoxy and substituted alkoxy, mono-, di- or oligosaccharide, and alkylideneoxy taken together with R 7′  when R 7′  is not H, provided that one of R 6  and R 6′  must be H but R 6  and R 6  may not both be H; and  
         R 7  and R 7′  are selected from the group consisting of H, acyl having from 1 to 8 carbon atoms, C 1  to C 20  alkyl, aryl, and alkylidene taken together with an adjacent R 6 , R 6′ , R 7  or R 7′ .  
       
     
     
         10 . A process for the preparation of a combinatorial library of compounds of the structure I, comprising contacting one or more azides of the structure IA:  
       
         
           
           
               
               
           
         
         wherein R is selected from the group consisting of hydrogen, hydroxy, alkoxy having up to 8 carbon atoms, acyloxy having up to 8 carbon atoms, acylamino having up to 8 carbon atoms, C 1  to C 20  hydrocarbyl and substituted hydrocarbyl and amino; n and n′ are, independently, 4 or 5, and m is 0 or 1 with one or more compounds of the structure IB  
         
           
             
             
                 
                 
             
           
         
         wherein R is as described above and R 3  is selected from the group consisting of H, C 1  to C 20  hydrocarbyl and substituted hydrocarbyl.  
       
     
     
         11 . A process according to  claim 10  for the preparation of a combinatorial library of compounds of the structure II, comprising contacting one or more compounds of the structure IIA:  
       
         
           
           
               
               
           
         
       
       wherein 
 R 1  is selected from the group consisting of H, Na, and C 1 -C 20  alkyl,  
 R 2  is selected from the group consisting of hydroxy, alkoxy having from 1 to 8 carbon atoms, acyloxy having from 1 to 8 carbon atoms, acylamino having from 1 to 8 carbon atoms, amino, hydrogen, and guanidino;  
 R 3  is selected from the group consisting of H, C 1  to C 20  hydrocarbyl and substituted hydrocarbyl; and  
 R 4  is selected from the group consisting of H, acyl having from 1 to 8 carbon atoms, alkyl having 1 to 20 carbon atoms; with one or more compounds of the structure IIB  
                     
 wherein R 3  is selected from the group consisting of H, C 1  to C 20  hydrocarbyl and substituted hydrocarbyl;  
 R 6  and R 6′  are selected from the group consisting of H, OH, C 1  to C 20  alkoxy and substituted alkoxy, mono-, di- or oligosaccharide, and alkylideneoxy taken together with R 7′  when R 7′  is not H, provided that one of R 6  and R 6′  must be H but R 6  and R 6′  may not both be H; and  
 R 7  and R 7′  are selected from the group consisting of H, acyl having from 1 to 8 carbon atoms, C 1  to C 20  alkyl, aryl, and alkylidene taken together with an adjacent R 6 , R 6′ , R 7  or R 7′ .  
 
     
     
         12 . A process according to  claim 10  for the preparation of a combinatorial library of compounds of the structure III, comprising contacting one or more compounds of the structure IIIA:  
       
         
           
           
               
               
           
         
       
       wherein 
 R 8  is selected from the group consisting of H, alkyl, said alkyl having from 1 to 20 carbon atoms, and acyl, said acyl group having from 1 to 8 carbon atoms;  
 with one or more compounds of the structure IIB  
                     
 wherein R3 is selected from the group consisting of H, C 1  to C 20  hydrocarbyl, and substituted hydrocarbyl;  
 R 6  and R 6  are selected from the group consisting of H, OH, C 1  to C 20  alkoxy and substituted alkoxy, mono-, di- or oligosaccharide, and alkylideneoxy taken together with R 7′  when R 7′  is not H, provided that one of R 6  and R 6′  must be H but R 6  and R 6  may not both be H; and  
 R 7  and R 7′  are selected from the group consisting of H, acyl having from 1 to 8 carbon atoms, C 1  to C 20  alkyl, aryl, and alkylidene taken together with an adjacent R 6 , R 6′ , R 7  or R 7′ .  
 
     
     
         13 . Acetylenic compounds of the structure IB  
       
         
           
           
               
               
           
         
         wherein R is selected from the group consisting of hydrogen, hydroxy, alkoxy having up to 8 carbon atoms, acyloxy having up to 8 carbon atoms, acylamino having up to 8 carbon atoms, C 1  to C 20  hydrocarbyl, substituted hydrocarbyl and amino; and R 3  is selected from the group consisting of H, C 1  to C 20  hydrocarbyl and substituted hydrocarbyl.  
       
     
     
         14 . Acetylenic compounds according to  claim 13  of the structure IIB  
       
         
           
           
               
               
           
         
         wherein R 3  is selected from the group consisting of H, C 1  to C 20  hydrocarbyl and substituted hydrocarbyl;  
         R 6  and R 6′  are selected from the group consisting of H, OH, C 1  to C 20  alkoxy and substituted alkoxy, mono-, di- or oligosaccharide, and alkylideneoxy taken together with R 7′  when R 7′  is not H, provided that one of R 6  and R 6′  must be H but R 6  and R 6′  may not both be H; and  
         R 7  and R 7′  are selected from the group consisting of H, acyl having from 1 to 8 carbon atoms, C 1  to C 20  alkyl, aryl, and alkylidene taken together with an adjacent R 6 , R 6′ , R 7  or R 7′ .