Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA.
Org Lett. 2011 Mar 4;13(5):1186-9. doi: 10.1021/ol200071p. Epub 2011 Feb 9.
Selective oxidation by bis[(trifluoroacetoxy)iodo]benzene (BTI) provides an effective trap for quenching adducts formed reversibly between dC and an ortho-quinone methide (QM) under physiological conditions. A model adduct generated by 4-methyl-o-QM and 2'-deoxycytidine is rapidly converted by intramolecular cyclization and loss of aromaticity to a characteristic product for quantifying QM alkylation. However, BTI induces a surprising rearrangement driven by overoxidation of a derivative lacking an alkyl substituent at the 4-position of the QM.
双[(三氟乙酰氧基)碘]苯（BTI）的选择性氧化为在生理条件下可逆形成的 dC 和邻醌甲醚（QM）之间的加合物提供了一种有效的淬灭剂。由 4-甲基-o-QM 和 2'-脱氧胞苷生成的模型加合物通过分子内环化和失去芳香性迅速转化为用于定量 QM 烷基化的特征产物。然而，BTI 会引起令人惊讶的重排，这是由 QM 缺少 4-位烷基取代基的衍生物过度氧化驱动的。
