cis-Tetrahydrofuran-3,4-diol structure as a key skeleton of new protecting groups removable by self-cyclization under oxidative conditions.
A variety of carbonate-type acyl groups having a cis-tetrahydrofuran-3,4-diol (1,4-anhydroerythritol) backbone structure and a TrS or MMTrS group have been examined as new "protected" protecting groups of the 5'-hydroxyl group of nucleosides. These acyl groups were designed in a manner where they could be deprotected by I(2)-promoted removal of the TrS or MMTrS group followed by self-cyclization involving an intramolecular attack of the once-generated neighboring hydroxyl group on the acyl carbon. It turned out that these acyl groups could be introduced into the 5'-hydroxyl group of a 3'-O-protected thymidine derivative by use of the corresponding acyl imidazolides or 4-nitrophenyl esters as well as by reaction with carbonyldiimidazole or 4-nitrophenyl chloroformate. Among the acyl groups tested, it was found that the CTFOC group could be easily introduced into the 5'-hydroxyl group of 3'-masked deoxyribonucleoside derivatives and rapidly removed under mild conditions using iodine.
Utagawa
Eri
E
Department of Life Science, Tokyo Institute of Technology, 4259 Nagatsuta, Yokohama 226-8501, Japan.
Sekine
Mitsuo
M
Seio
Kohji
K
D000215:Acylation; D000438:Alcohols / Q000737:chemistry; D003500:Cyclization; D005663:Furans / Q000737:chemistry*; D009705:Nucleosides; D010084:Oxidation-Reduction; D013936:Thymidine
D000438:Alcohols; D005663:Furans; D009705:Nucleosides; D013936:Thymidine