Abstract

Massarinolin A and the purpurolides are bioactive bergamotane sesquiterpenes containing a complex tetracyclic skeleton. In their Communication on page 24828, Mingji Dai and co-workers report a divergent and enantioselective approach to complete the first total syntheses of five tetracyclic bergamotane sesquiterpenes, which also led to a structural revision of massarinolin A. Their approach features a scalable flow photochemical Wolff rearrangement to build the challenging bicyclo[3.1.1]heptane core and a furan oxidative cyclization to form the oxaspirolactone moiety.

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