Chizhova Maria, Khoroshilova Olesya, Dar'in Dmitry, Krasavin Mikhail
Saint Petersburg State University , Saint Petersburg , 199034 Russian Federation.
J Org Chem. 2018 Oct 19;83(20):12722-12733. doi: 10.1021/acs.joc.8b02164. Epub 2018 Sep 28.
In the course of synthesizing and testing various "azole-including" cyclic anhydrides in the Castagnoli-Cushman reaction with imines, a remarkably reactive, pyrrole-based anhydride has been identified. It displayed a remarkably efficient reaction with N-alkyl and N-aryl imines, in particular, with "enolizable" α-C-H imines which typically fail to react with a majority of known cyclic anhydrides. The reactivity of this anhydride has been justified by an efficient resonance stabilization of its enol form. This finding expands the existing arsenal of highly reactive cyclic anhydrides and further confirms the importance of anhydride enolization for an efficient Castagnoli-Cushman reaction.
在与亚胺进行卡斯塔尼奥利-库什曼反应中合成和测试各种“含唑”环状酸酐的过程中，一种具有显著反应活性的吡咯基酸酐被鉴定出来。它与N-烷基和N-芳基亚胺，特别是与“可烯醇化的”α-C-H亚胺表现出非常高效的反应，而这些亚胺通常无法与大多数已知的环状酸酐发生反应。这种酸酐的反应活性通过其烯醇形式的有效共振稳定作用得到了解释。这一发现扩展了现有的高反应活性环状酸酐库，并进一步证实了酸酐烯醇化对于高效的卡斯塔尼奥利-库什曼反应的重要性。
