Reaction of α-Diazopyrroles with Enamines: Synthesis of Pyrrolo[2,1-c][1,2,4]triazines and α-(1,2,5-Triazapenta-1,3-dienyl)pyrroles,The Journal of Organic Chemistry

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Reaction of α-Diazopyrroles with Enamines: Synthesis of Pyrrolo[2,1-c][1,2,4]triazines and α-(1,2,5-Triazapenta-1,3-dienyl)pyrroles
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2022-07-08 , DOI: 10.1021/acs.joc.2c01102
Nikita A Kaminskiy ₁ , Ekaterina E Galenko ₁ , Mariya A Kryukova ₁ , Mikhail S Novikov ₁ , Alexander F Khlebnikov ₁

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α-Diazopyrroles selectively react with enamines at room temperature to give either (4+2)-cycloaddition–dehydroamination cascade products, pyrrolo[2,1-c][1,2,4]triazines, or azo coupling products. The reaction was used for the synthesis of functionalized ortho-fused heterocycles with new tetrahydrobenzo[e]pyrrolo[2,1-c][1,2,4]triazine and tetrahydro-6H-cyclohepta[e]pyrrolo[2,1-c][1,2,4]triazine frameworks. Unstable azo compounds, 2-[(2-aminovinyl)diazenyl]pyrroles, were obtained from enamines of tetralone or acyclic ketones. According to the density functional theory calculations, (4+2)-cycloaddition of α-diazopyrroles with enamines proceeds in a nonconcerted manner via the zwitterionic intermediate, which undergoes cyclization to pyrrolotriazine or a competitive 1,5-prototropic shift leading to the formation of azo coupling product.

中文翻译：

α-重氮吡咯与烯胺的反应：吡咯并[2,1-c][1,2,4]三嗪和α-(1,2,5-Triazapenta-1,3-二烯基)吡咯的合成

α-重氮吡咯在室温下选择性地与烯胺反应生成 (4+2)-环加成-脱氢胺级联产物、吡咯并[2,1- c ][1,2,4]三嗪或偶氮偶联产物。该反应用于与新的四氢苯并[ e ]吡咯并[2,1- c ][1,2,4]三嗪和四氢-6H-环庚[ e ]吡咯并[2,1]合成官能化的邻位稠合杂环-c _][1,2,4]三嗪框架。从四氢萘酮或无环酮的烯胺中获得不稳定的偶氮化合物，2-[(2-氨基乙烯基)二氮烯基]吡咯。根据密度泛函理论计算，α-重氮吡咯与烯胺的 (4+2)-环加成通过两性离子中间体以非协调方式进行，中间体环化为吡咯并三嗪或竞争性 1,5-质子转变导致形成偶氮偶联产物。

更新日期：2022-07-08

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