Abstract
Main observation and conclusionThe first transition metal‐free highly stereoselective positional isomerization of various α‐alkyl styrenes through a carbocation mechanism triggered strategy is developed by using Al(OTf)3 as a hidden Brønsted acid catalyst, which provides facile access to value‐added acyclic tri‐ and tetra‐substituted alkenes in good yields with high stereoselectivity under mild conditions. The practicality of this protocol is further highlighted by the gram‐scale synthesis, high stereoselectivity, good functional group tolerance, and simple operation. Mechanistic studies support that Al(OTf)3 acts as a hidden Brønsted acid catalyst and a carbocation intermediate is formed.
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