Abstract

One thing leads to another: Bis(benzannelated) 5,6-spiroketal skeletons can be constructed by an efficient cascade process involving an unprecedented CuI-catalyzed intramolecular alkyne hydroalkoxylation and an asymmetric hetero-Diels–Alder cycloaddition. The method yields a series of diversely functionalized spiroketals from two readily available open-chained starting materials in good yields and excellent diastereoselectivities.

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