摘要
采用密度泛函理论方法对3,4-二-O-乙酰基-L-阿拉伯烯糖与HR—CH2—CH=CH2(R=O,CH2,NH,S)反应的Ferrier重排反应机理进行了研究,并通过自洽场极化连续模型(PCM)模拟了苯和二氯化碳溶剂对反应历程的影响,计算了相应结构的单点能,考虑了2条可能的反应途径,获得了较优反应途径和反应速率控制步骤.研究表明:苯和二氯化碳溶剂的溶剂效应未对反应历程产生明显影响.R基电负性越大、体积越大以及H+的存在,均有利于该重排反应进行.
Theoretical study on the rearrangement mechanism of 3,4-di-O-acetyl-L-glucal with HR—CH2—CH=CH2（R=O,CH2,NH,S） was carried out by density functional theory（DFT）,and the solvent of benzene and CH2Cl2 were evaluated using polarizable continuum model（PCM） through the single point energy calculated.Two pathways were considered,favorable pathway and the rate-limiting process were determined.The solvent effect of solvent is not distinct for the reaction.More electronegative,greater volume and exist of H＋ are favor of the reaction.
出处
《分子科学学报》
CAS
CSCD
北大核心
2012年第5期401-407,共7页
Journal of Molecular Science
基金
国家自然科学基金资助项目(20873055)
河北北方学院青年基金资助项目(Q201105)
