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Theoretical Study of 1,3-Dipolar Cycloaddition of Hydrazoic Acid to Substituted Ynamines
Xiao-fang Chen,Kun Yang,Ke-li Han *
Author NameAffiliationE-mail
Xiao-fang Chen State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China  
Kun Yang State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China  
Ke-li Han * State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China klhan@dicp.ac.cn 
Abstract:
The 1,3-dipolar cycloaddition reactions of various substituted ynamines with hydrazoic acid were theoretically investigated with the high-accuracy CBS-QB3 method. Two regioisomers,4-amine, and 5-amine substituted adducts, were obtained, with the former as the preferred yield. This regioselectivity is rationalized by the frontier molecular orbital theory.The reactivity and synchronicity are enhanced with the increase of the electron-withdrawing character of the substitute on ynamine fragment. The calculations also show that the effect of solvent increases the activation energy, and the reaction becomes even harder in polar solvent.
Key words:  1,3-dipolar cycloaddition, Hydrazoic acid, Internal alkyne, CBS-QB3, Solvent effect, Substituent effect, Frontier molecular orbital theory
FundProject:
Theoretical Study of 1,3-Dipolar Cycloaddition of Hydrazoic Acid to Substituted Ynamines
陈晓芳,杨昆,韩克利 *
摘要:
采用高精度CBS-QB3方法对一系列取代炔胺与叠氮酸之间的1,3环加成反应进行了理论研究. 该反应生成两种区域选择性异构体,它们分别是4-取代和5-取代加成物,其中以5-取代加成物为优势产物. 此区域选择性由前线分子轨道理论给出了合理解释.该反应的活性和协同性随着取代炔胺的取代基吸电子能力增加而增加. 计算结果也表明,溶剂效应使叠氮酸与取代炔胺的1,3环加成反应的活化能垒增加,在极性溶剂下,该反应变得难以进行.
关键词:  环加成,叠氮酸,从头计算
DOI:10.1088/1674-0068/22/02/143-148
分类号: