中国科学院上海有机化学研究所机构知识库
Advanced  
SIOC OpenIR  > 中科院有机氟化学重点实验室  > 期刊论文
学科主题: 氟化学 ; 生命有机化学
题名: Synthesis and conformational analysis of D-2 '-deoxy-2 ',2 '-difluoro-4 '-dihydro-4 '-thionucleosides
其他题名: D-2-脱氧-2,2-二氟-4-二氢-4-核苷的合成和构象分析
作者: Zheng F(郑峰) ; Lin F(林赋) ; Wang RX(王任小) ; Qing FL(卿凤翎)
通讯作者: 卿凤翎
刊名: Org. Biomol. Chem.
发表日期: 2010
卷: 8, 期:1, 页:163-170
收录类别: SCI
部门归属: 中国科学院上海有机化学研究所
英文摘要: An efficient synthesis of D-2'-deoxy-2',2'-difluoro-4'-dihydro-4'-thionucleosides is described. The conformations of D-2'-deoxy-2', 2'-difluoro-4'-dihydro-4'-thiouridine were studied by X-ray crystallography, NMR spectroscopy and molecular modeling in an attempt to explore the roles of the two gem-difluorine atoms in the puckering preferences of the thiosugar ring. No matter which conformation (south or north) the thiosugar adopts, there is always one fluorine in a pseudoaxial position, with the other in a pseudoequitorial position and thus the strong antiperiplanar (ap) effects from C-H and C-C sigma-bonds to sigma*C-F are equal to each other in these two conformers. Therefore, the other weak effects, such as dipole-dipole interactions and electrostatic attractions, become more important for determining the overall conformation of the sugar ring. Based on the results of NMR spectroscopy, high-level quantum computations and molecular dynamic simulations were performed to study the preferred pucker of the thiosugar ring in solution. Our results showed that the strong antiperiplanar preference of C-H and C-C sigma-bonds to sigma*C-F and sigma*C-O seemed to be responsible for the favored S-conformation in solution, and the weak electrostatic attractions between (delta+)C2-F beta(delta-) and (delta+)H6-C6(delta-) may stabilize the preferred structure further, and keep the base moiety in a high anti-rotamer population in solution. In contrast, the packing forces (hydrogen bond OH center dot center dot center dot O=C, dipole-dipole interaction C-F center dot center dot center dot C=O) in the solid state compensated the energetic disadvantage of the relatively less stable N-conformation, and drove the thiouridine to crystallize in the N-conformation. These results, along with the earlier empirical rules regarding proton chemical shifts in carbohydrates and nucleosides, were used to propose a method based on proton chemical shifts for the analysis of the N (sic) S equilibrium of the fluorinated sugar ring.
语种: 英语
相关网址: 查看原文
WOS记录号: WOS:000272613300024
Citation statistics:
内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/17693
Appears in Collections:中科院有机氟化学重点实验室_期刊论文

Files in This Item: Download All
File Name/ File Size Content Type Version Access License
2010452.pdf(341KB)----开放获取--View Download

Recommended Citation:
Zheng F,Lin F,Wang RX,et al. Synthesis and conformational analysis of D-2 '-deoxy-2 ',2 '-difluoro-4 '-dihydro-4 '-thionucleosides[J]. Org. Biomol. Chem.,2010,8(1):163-170.
Service
Recommend this item
Sava as my favorate item
Show this item's statistics
Export Endnote File
Google Scholar
Similar articles in Google Scholar
[郑峰]'s Articles
[林赋]'s Articles
[王任小]'s Articles
CSDL cross search
Similar articles in CSDL Cross Search
[郑峰]‘s Articles
[林赋]‘s Articles
[王任小]‘s Articles
Related Copyright Policies
Null
Social Bookmarking
Add to CiteULike Add to Connotea Add to Del.icio.us Add to Digg Add to Reddit
文件名: 2010452.pdf
格式: Adobe PDF
此文件暂不支持浏览
所有评论 (0)
暂无评论
 
评注功能仅针对注册用户开放,请您登录
您对该条目有什么异议,请填写以下表单,管理员会尽快联系您。
内 容:
Email:  *
单位:
验证码:   刷新
您在IR的使用过程中有什么好的想法或者建议可以反馈给我们。
标 题:
 *
内 容:
Email:  *
验证码:   刷新

Items in IR are protected by copyright, with all rights reserved, unless otherwise indicated.

 

 

Valid XHTML 1.0!
Powered by CSpace