Diarylsulfide backbone containing photolabile protecting groups

Abstract

The present disclosure relates to photoactivable protecting groups containing a diarylsulfide chromophore, a method for the synthesis thereof and their use as photoactivable protecting groups using maskless photolithography based array synthesis.

What is claimed is: 
     
         1 . A compound of the formula 
       
         
           
           
               
               
           
         
         wherein Y is S or O, and 
         A is selected from the group consisting of —CH 2 —, —CH 2 —CH 2 —, —CH(CH 3 )—, —CH(CH 3 )—CH 2 —, and 
         R1 is an unsubstituted or substituted aryl- or heteroaryl-group, and R3 is H, a methyl group or an ethyl group, and 
         wherein R2 is H, a phosphoramidite, H-phosphonate or phosphate triester, or 
         wherein R2 is 
       
       
         
           
           
               
               
           
         
         or wherein R2 is 
       
       
         
           
           
               
               
           
         
         wherein R4 is H, a phosphoramidite, H-phosphonate or phosphate triester, and 
         wherein R5 is H, OH, a halogen or XR6, wherein X is O or S and R6 is H, an alkyl-group, aryl-group, or OR6 is a phosphoramidite, phosphodiester, phosphotriester, H-phosphonate or an acetal or silicone moiety, and 
         wherein B is selected from the group consisting of adenine, cytosine, guanine, thymine, uracil, 2,6-diaminopurine-9-yl, hypoxanthin-9-yl, 5-methylcytosinyl-1-yl, 5-amino-4-imidazolecarboxylic acid-1-yl or 5-amino-4-imidazolecarboxylic acid amide-3-yl, wherein when B is adenine, cytosine or guanine the primary amino group optionally has a protecting group or when B is thymine or uracil at the O 4  position is optionally a protecting group, or 
         wherein R 2  is 
       
       
         
           
           
               
               
           
         
         wherein R7 is a natural amino acid, a non-natural amino acid or an amino acid derivative having a urethan bond to formula Ib, or 
         wherein formula IV represents the carboxy function of a natural amino acid, a non-natural amino acid or an amino acid derivative, having an ester bond to formula Ib. 
       
     
     
         2 . The compound according to  claim 1  wherein R1 is a phenyl-group, a tert-butyl-phenyl group, a 1- or 2-naphthyl-group, a 2-pyridyl-group an aminophenyl-group, an N-alkylaminophenyl-group, an N-Acylaminophenyl-group, a carboxyphenyl-group, a phenylcarboxylic ester or an amide. 
     
     
         3 . The compound according to  claim 1  wherein A is —CH(CH 3 )—CH 2 —. 
     
     
         4 . The compound according to  claim 1  wherein R2 is a phosphoramidite or —P(OCH 2 CH 2 CN)(N-iPr 2 ). 
     
     
         5 . The compound according to  claim 1  wherein R3 is H or an ethyl group. 
     
     
         6 . The compound according to  claim 1  wherein R4 is H and R5 is H. 
     
     
         7 . The compound according to  claim 1  wherein B is selected from the group consisting of adenine, cytosine, guanine, thymine or uracil. 
     
     
         8 . The compound according to  claim 1  wherein when B is adenine, cytosine or guanine the protecting group is phenoxyacetyl-, 4-tert-butyl-phenoxyacetyl-, 4-isopropyl-phenoxyacetyl- or dimethylformamidino-residues, when B is adenine the protecting group is benzoyl- or p-nitro-phenyl-ethoxy-carbonyl-(p-NPPOC)-residues, when B is guanine the protecting group is isobutyroyl-, p-nitrophenylethyl (p-NPE) or p-NPEOC-residues and when B is cytosine the protecting group is benzoyl-, isobutyryl- or p-NPEOC-residues. 
     
     
         9 . The compound according to  claim 1  wherein R7 is a natural amino acid. 
     
     
         10 . The compound of  claim 1  wherein Y is S; A is —CH(CH3)CH2-; R1 is phenyl; R2 is H; and R3 is ethyl.