Abstract
A readily available oxo‐ReVcatalyst has been shown to promote a one‐pot multistep process that involves the Meyer–Schuster rearrangement of alkynols followed by the Diels–Alder cycloaddition of the resulting enones. These reactions were performed under mild conditions in the presence of 5 mol‐% of the catalyst to afford the cycloadducts in good yields with almost 100 %endostereoselectivity. In‐depth computational studies of the cycloaddition mechanism provided the preferred geometry of the rhenium complex in the transition state (TS) and corroborated the experimental endo selectivity.
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