Bidusenko Ivan A, Schmidt Elena Yu, Kozlova Darya O, Protsuk Nadezhda I, Ushakov Igor A, Bagryanskaya Irina Yu, Orel Vladimir B, Zubarev Andrey A, Trofimov Boris A
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russia.
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk 630090, Russia.
Org Lett. 2024 Jun 14;26(23):4963-4968. doi: 10.1021/acs.orglett.4c01531. Epub 2024 May 31.
Di(het)aryldiynes smoothly react with -benzylaldimines in a [4 + 3] cycloaddition manner under the action of the KOBu/DMSO system (60 °C, 30 min) to afford pharmaceutically relevant tetra(het)arylsubstituted 3-azepines in up to 71% yield. The process involves the addition of azaallyl anions to one of the triple bonds of diynes followed by prototropic isomerization and cyclization of anionic intermediates with participation of the second triple bond. The cascade mechanism is consistent with quantum-chemical analysis (B2PLYP-D3/6-311+G**//B3LYP-D3/6-31+G* + PCM).
在KOBu/DMSO体系（60℃，30分钟）作用下，二（杂）芳基二炔与苄基亚胺以[4 + 3]环加成方式顺利反应，以高达71%的产率得到药学相关的四（杂）芳基取代的3 - 氮杂环庚烷。该过程包括氮杂烯丙基阴离子加成到二炔的一个三键上，随后进行质子转移异构化以及阴离子中间体在第二个三键参与下的环化。该串联机理与量子化学分析（B2PLYP - D3/6 - 311 + G**//B3LYP - D3/6 - 31 + G* + PCM）一致。
