Chemoselective electrochemical seleno-cyclization of dienes to me dium-size d b enzo[ b ]azocines

The preparation of medium-sized benzo[ b ]azocines has always been challenging because of inherently unfavorable enthalpy and entropy factors. This report presents a novel approach for accessing 8membered seleno-benzo[ b ]azocines via electrochemically-driven seleno-cyclization. This method enables room-temperature preparation of various structurally diverse medium-sized seleno-benzo[ b ]azocines. The facile deselenation of the seleno-cyclization products to generate functionalized dienes is an additional benefit of this indispensable reaction. Mechanistic insights are presented based on radical inhibition experiments and cyclic voltammetry measurements, which elucidate the radical pathway. Finally, density functional theory calculations further rationalize the rate-determining step and the unique chemoselectivity observed in this transformation.(c) 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Automated summary

This study presents a novel method for the preparation of medium-sized seleno-benzo[ b ]azocines via electrochemical reaction, demonstrating its advantages in producing structurally diverse compounds and facile deselenation to generate functionalized dienes. Mechanistic insights provided by radical inhibition experiments and cyclic voltammetry measurements, along with density functional theory calculations, offer a better understanding of the reaction pathway and its rate-determining step and unique chemoselectivity.