A readily available oxo‐ReV catalyst 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 % endo stereoselectivity. 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.

No abstract

No abstract

No abstract