Computational studies of Brønsted acid-catalyzed transannular cycloadditions of cycloalkenone hydrazones

Abstract

The contribution to the energy barrier of a series of tethers in transannular cycloadditions of cycloalkenes with hydrazones has been computationally studied by using DFT. The Houk's distortion model has been employed to evaluate the influence of the tether in the cycloaddition reaction. That model has been extended to determine the contribution of each tether and, more importantly, the effect exerted between them. In addition to the distortion induced by the tethers, the entropy effects caused by them has also been studied. The analysis of the evolution of the electron localization function along the reaction revealed the highly concerted character of the reaction.

Catalytic multi-step domino and one-pot reactions

“…Computational studies of transannular cycloadditions of cycloalkenone hydrazones catalyzed by BINOL-derived phosphoric acid are reported in the Full Research Paper by Vicario, Merino, and co-workers [ 10 ]. Their methodologies can now be used to predict the reactivity of different substrates in other cycloaddition reactions through concerted or stepwise mechanisms.…”