In-depth insight into structure-reactivity/regioselectivity relationship of Lewis acid catalyzed cascade 4πe-cyclization/dicycloexpansion reaction.

ABSTRACT: The Lewis acid-catalyzed tittle reaction of 1,3-dicycloalkenlidine ketones is recognized as so far the shortest and most effective 1-step method for construction of angular tricyclic scaffolds, which are extensively found in bioactive terpenoids. Here, a further kinetic study of this reaction with 30 reaction examples is carried out using in situ IR technology and DFT calculation. That enables the creation of well-fitted linear relationships of lnk/(ΔG₁^‡/T), ΔG₁^‡/ΔG₂, ln(k/k_H)/σ_p, reflecting the structure's effect on reactivity/selectivity, and validating the reaction mechanism. Particularly highlighted is that substituents C1-R¹/C3-R² activate this reaction in the order: alkyl ≈ aryl >> aryl

SUBMITTER: Lu K 

PROVIDER: S-EPMC11923253 | biostudies-literature | 2025 Mar

REPOSITORIES: biostudies-literature