双环和三环4-N-氨基甲酰基脱氧胞苷衍生物的合成及荧光性质

Synthesis and fluorescent properties of bi- and tricyclic 4-N-carbamoyldeoxycytidine derivatives.

作者信息

Miyata Kenichi, Mineo Ryota, Tamamushi Ryuji, Mizuta Masahiro, Ohkubo Akihiro, Taguchi Haruhiko, Seio Kohji, Santa Tomofumi, Sekine Mitsuo

机构信息

Department of Life Science and Division of Collaborative Research for Bioscience and Biotechnology, Frontier Collaborative Research Center, Tokyo Institute of Technology, 4259 Nagatsuta, Midoriku, Yokohama 226-8501, Japan.

出版信息

J Org Chem. 2007 Jan 5;72(1):102-8. doi: 10.1021/jo0617767.

DOI:10.1021/jo0617767

PMID:17194087

Abstract

New bi- and tricyclic deoxycytidine derivatives (dChpd, dCmpp, dCtpp, dCppp) were synthesized as analogues of a fluorescent nucleoside, dChpp, previously reported. The carbamoyl group of dChpd and the 5-position of the cytosine ring are bridged via an ethylene linker so that the modified group forms a nonplanar structure with the cytosine ring. The fluorescent study of dChpd indicated that the coplanar structure between the carbamoyl group and the cytosine ring is of importance. N-Methylation of the carbamoyl group (dCmpp) weakened the intensity of the fluorescence of dChpp, and the derivative (dCtpp), which had a thiocarbamoyl group, lost its fluorescent property. Moreover, addition of a pyrrolo-ring (dCppp) to dChpp enhanced the intensity of fluorescence, and an emission light was observed with a marked Stokes shift of 120 nm.

摘要

新型双环和三环脱氧胞苷衍生物（dChpd、dCmpp、dCtpp、dCppp）作为先前报道的荧光核苷dChpp的类似物被合成出来。dChpd的氨基甲酰基与胞嘧啶环的5位通过一个亚乙基连接桥相连，使得修饰基团与胞嘧啶环形成一个非平面结构。dChpd的荧光研究表明，氨基甲酰基与胞嘧啶环之间的共平面结构很重要。氨基甲酰基的N-甲基化（dCmpp）减弱了dChpp的荧光强度，而具有硫代氨基甲酰基的衍生物（dCtpp）失去了荧光特性。此外，在dChpp上添加一个吡咯环（dCppp）增强了荧光强度，并且观察到发射光具有120 nm的显著斯托克斯位移。