Diarylsulfide backbone containing photolabile protecting groups
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.
1. A compound of the formula
wherein Y is S, 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
or wherein R2 is
wherein R4 is H, forms 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 forms 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.
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.
3. The compound according to claim 1 wherein A is —CH(CH 3 )—CH 2 —.
4. The compound according to claim 1 wherein R3 is H or an ethyl group.
5. The compound according to claim 1 wherein R4 is H and R5 is H.
6. The compound according to claim 1 wherein B is selected from the group consisting of adenine, cytosine, guanine, thymine or uracil.
7. 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.
8. The compound according to claim 1 wherein R7 is a natural amino acid.
9. The compound of claim 1 wherein Y is S; A is —CH(CH 3 )CH 2 —; R1 is phenyl, tert-butyl-phenyl, 1- or 2-naphtyl or 2-pyridyl; and R3 is H or ethyl.