Theoretical Study of 1,3-Dipolar Cycloaddition of Hydrazoic Acid to Substituted Ynamines
- Received Date: 2009-01-23
- 1,3-dipolar cycloaddition, Hydrazoic acid, Internal alkyne, CBS-QB3, Solvent effect, Substituent effect, Frontier molecular orbital theory
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.
|Citation:||Xiao-fang Chen, Kun Yang, Ke-li Han . Theoretical Study of 1,3-Dipolar Cycloaddition of Hydrazoic Acid to Substituted Ynamines[J]. Chinese Journal of Chemical Physics , 2009, 22(2): 143-148. doi: 10.1088/1674-0068/22/02/143-148|