Dual ReV Catalysis in One-Pot Consecutive Meyer–Schuster and Diels–Alder Reactions

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 reac- tions 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 com- putational studies of the cycloaddition mechanism provided the preferred geometry of the rhenium complex in the transi- tion state (TS) and corroborated the experimental endo select- ivity.