Uchiyama Naoki, Ogata Toshihiko, Oka Natsuhisa, Wada Takeshi
Department of Medical Genome Sciences, Graduate School of Frontier Sciences, The University of Tokyo, Chiba, Japan.
Nucleosides Nucleotides Nucleic Acids. 2011 Jun;30(6):446-56. doi: 10.1080/15257770.2011.592171.
Arylmethyl groups such as benzyl, p-methoxybenzyl, and 1-pyrenylmethyl groups were introduced to the 2'-O-position of nucleosides by reductive etherification. Combining corresponding aromatic aldehydes with 2'-O-trimethylsilylnucleoside derivatives in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) resulted in moderate to good yields of the 2'-O-arylmethyluridine derivatives, whereas the corresponding cytidine and adenosine derivatives were obtained in low yields. The reaction of ribonucleosides with aliphatic aldehydes did not proceed smoothly. Anomerization of the uridine derivatives by TMSOTf was observed in CH(2)Cl(2), toluene, and CH(3)CN, but was completely suppressed when the reactions were conducted in 1,4-dioxane.
通过还原醚化反应，将芳甲基如苄基、对甲氧基苄基和1-芘甲基引入核苷的2'-O-位。在三氟甲磺酸三甲基硅酯（TMSOTf）存在下，使相应的芳香醛与2'-O-三甲基硅烷基核苷衍生物反应，可得到中等至良好产率的2'-O-芳甲基尿苷衍生物，而相应的胞苷和腺苷衍生物产率较低。核糖核苷与脂肪醛的反应进行得并不顺利。在二氯甲烷、甲苯和乙腈中观察到TMSOTf会使尿苷衍生物发生异头化，但在1,4-二氧六环中进行反应时，这种异头化被完全抑制。
