Schnell Simon D, Schilling Mauro, Sklyaruk Jan, Linden Anthony, Luber Sandra, Gademann Karl
Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057 Zurich, Switzerland.
Org Lett. 2021 Apr 2;23(7):2426-2430. doi: 10.1021/acs.orglett.0c04113. Epub 2021 Mar 11.
The nucleophilic addition of silyl-enol ethers to nitrogen in 3-monosubstituted s-tetrazines mediated by BF is reported. The preference for this azaphilic addition over the usually observed inverse electron demand Diels-Alder reactions was evaluated theoretically and corroborated by experiments. The substrate dependency of this unusual reaction was rationalized by determination of the activation barriers and on the basis of the activation strain model by employing density functional theory.
报道了在BF介导下，硅烯醇醚对3-单取代s-四嗪中氮的亲核加成反应。通过理论评估了这种亲氮加成相对于通常观察到的反常电子需求狄尔斯-阿尔德反应的偏好，并通过实验得到了证实。利用密度泛函理论，通过测定活化能垒并基于活化应变模型，对这种异常反应的底物依赖性进行了合理解释。
