通过炔烃环化反应构建含两个内嵌七元环的1,4-二氢吡咯并[3,2-]吡咯类化合物

Sanil Gana, Dobrzycki Łukasz, Cyrański Michał K, Jacquemin Denis, Chaładaj Wojciech, Gryko Daniel T

Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland.

Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland.

J Org Chem. 2025 Jan 10;90(1):614-622. doi: 10.1021/acs.joc.4c02538. Epub 2024 Dec 31.

Drastic changes to the character of the acidic catalyst enable the reversal of the double alkyne benzannulation reaction output. In the presence of a strong Brønsted acid, 1,4-dihydropyrrolopyrroles undergo transformation which results in the formation of two 7-membered rings. Computational studies imply that the thermodynamically unfavored 7-membered ring is forged via the kinetically favored attack of a protonated alkyne at the position 3a of pyrrolopyrrole followed by a 1,2-vinyl shift.

酸性催化剂性质的剧烈变化能够逆转双炔苯并环化反应的产物。在强布朗斯特酸存在的情况下，1,4 - 二氢吡咯并吡咯会发生转化，从而形成两个七元环。计算研究表明，热力学上不利的七元环是通过质子化炔烃在吡咯并吡咯3a位的动力学有利进攻，随后发生1,2 - 乙烯基迁移而形成的。