Abstract
Epoxide-opening polyether cascade cyclizations fascinate since the Nakanishi hypothesis was put forward to explain the biosynthesis of brevetoxin B. By now, violations of the Baldwin rules are as common as speeding on the highway, McDonald elegantly mastered the inversion of directionality, but how can trans epoxides cyclize into cis-fused rings? A simple shift from SN2-type to SN1-type oxonium opening could be the answer. The currently emerging pnictogen-bonding catalysis reveals a completely different and quite spectacular alternative. For more details see the Communication by S. Matile et al. on page 15471 ff.
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