Feofanov Mikhail, Akhmetov Vladimir, Sharapa Dmitry I, Amsharov Konstantin
Institute of Chemistry, Organic Chemistry, Martin-Luther-University Halle-Wittenberg, Kurt-Mothes-Strasse 2, D-06120 Halle, Germany.
Department of Chemistry and Pharmacy, Organic Chemistry II, Friedrich-Alexander University Erlangen-Nuernberg, Nikolaus-Fiebiger Str. 10, 91058 Erlangen, Germany.
Org Lett. 2020 Aug 7;22(15):5741-5745. doi: 10.1021/acs.orglett.0c01717. Epub 2020 Jun 17.
Herein, we show that biradical character and appropriate distribution of spin density can be used for synthetic purposes. We demonstrate the rational domino annulation that includes dehydrative π-extension (DPEX) as the initiation step and subsequent oxidative electrocyclizations (EC) promoted by favorable localization of the unpaired electrons enabling up to four C-C bonds formed during the reaction. Contradicting to the Woodward-Hoffmann rules, the reaction proceeds at room temperature, whereas termination occurs when biradical character vanishes.
在此，我们表明双自由基特性和自旋密度的适当分布可用于合成目的。我们展示了合理的多米诺环化反应，该反应以脱水π-扩展（DPEX）作为起始步骤，随后由未成对电子的有利定位促进氧化电环化（EC），使得反应过程中能够形成多达四个碳-碳键。与伍德沃德-霍夫曼规则相反，该反应在室温下进行，而当双自由基特性消失时反应终止。
