A computational study on the substituent effects and product stereoselectivity of the intermolecular formal aza-[3+3] cycloaddition reaction between vinylogous amides and α,β-unsaturated imine cations |
| |
Authors: | Yan Wang De-Cai Fang Ruo-Zhuang Liu |
| |
Institution: | aCollege of chemistry, Beijing Normal University, 19th Xin Wai St., Beijing 100875, China |
| |
Abstract: | The substituent effects and product stereoselectivity of the title reaction has been studied using density functional theory (DFT) calculations at the B3LYP/6-31G(d,p) level of theory. It was found that the substituents do not perturb the mechanism of intermolecular formal aza-3+3] cycloaddition. Our calculations also show that methyl or benzyl groups on the N atom of vinylogous amide favor the addition step, but alkyl substituents on the either N atom or terminal C atom of α,β-unsaturated imine cation have opposite effects. Alkyl substituents on the N atom of α,β-unsaturated imine cation may lower the activation barriers for elimination of amide. The steric interaction between two substituents leads to the formation of major product both thermodynamically and kinetically. |
| |
Keywords: | [3+3] Cycloaddition Vinylogous amide α β -Unsaturated imine cation DFT calculations Substituent effects Stereoselectivity |
本文献已被 ScienceDirect 等数据库收录! |