期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 74, 期 7, 页码 2726-2735出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo802822u
关键词
-
资金
- Ministerio de Ciencia e Innovacion of the Spanish Government [CTQ2006-14297/BQU]
The regioselective hetero-Diels-Alder (HDA) reaction of asymmetric tetrazines (TTZs) with electron-rich (ER) ethylenes has been studied with use of DFT methods at the B3LYP/6-31G* level of theory. The reaction is a domino process that comprises three consecutive reactions: (i) a HDA reaction between the TTZ and the ER ethylene; (ii) a retro-Diels-Alder reaction with loss of nitrogen; and (iii) a beta-hydrogen elimination with formation of the final pyridazines. The first polar HDA reaction, which is associated to the nucleophilic attack of the ER ethylene to the electrophilically activated TTZ, is the rate and regioselectivity determining step of the domino process. The unexpected regioselectivity of these HDA reactions is explained within the polar cycloaddition model by using the conceptual DFT. Although the nucleophilic attack of the ER ethylene over the para position relative to the methylsulfinyl substituent could favor the charge transfer, it is energetically more unfavorable because it diminishes the electron density at the electronegative TTZ core.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据