通过对胞嘧啶碱基进行N4-乙酰基保护实现环丁烷嘧啶二聚体的立体选择性形成。

Stereoselective formation of a cyclobutane pyrimidine dimer by using N4-acetyl protection of the cytosine base.

作者信息

Nishiguchi Kosuke, Yamamoto Junpei, Iwai Shigenori

机构信息

Division of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.

出版信息

Nucleic Acids Symp Ser (Oxf). 2008(52):437-8. doi: 10.1093/nass/nrn222.

DOI:10.1093/nass/nrn222

PMID:18776441

Abstract

The cytosine base in DNA undergoes hydrolytic deamination at a considerable rate when UV radiation induces formation of a cyclobutane pyrimidine dimer (CPD) with an adjacent pyrimidine base. As a part of our study on the synthesis of CPD-containing oligonucleotides, we have prepared properly-protected thymidylyl-(3' 5')-N(4)-acetyl-2'-deoxycytidine, and the solution of this compound was UV-irradiated using acetophenone as a sensitizer. In this reaction, hydrolysis of the acetylamino group occurred, and a trans-syn cyclobutane thymine-uracil dimer with the syn-anti conformation around the glycosidic bonds was formed stereoselectively.

摘要

当紫外线辐射诱导DNA中的胞嘧啶碱基与相邻嘧啶碱基形成环丁烷嘧啶二聚体（CPD）时，胞嘧啶碱基会以相当高的速率发生水解脱氨反应。作为我们关于含CPD寡核苷酸合成研究的一部分，我们制备了适当保护的胸苷酰基-(3'→5')-N(4)-乙酰基-2'-脱氧胞苷，并使用苯乙酮作为敏化剂对该化合物的溶液进行紫外线照射。在该反应中，乙酰氨基发生水解，并且立体选择性地形成了具有围绕糖苷键的顺式-反式构象的反式-顺式环丁烷胸腺嘧啶-尿嘧啶二聚体。