Enantioselective Total Synthesis of (−)‐Spiroxins A, C, and D

Spiroxins A, C, and D are metabolites that have been identified in the marine fungal strain LL‐37H248. Their unique polycyclic structures and intriguing biological activities make them attractive targets for the synthetic community. Based on a scalable enantioselective epoxidation of 5‐substituted naphthoquinone, an oxidation/spiroketalization cascade, ortho ‐selective chlorination of the phenol unit, and oxime‐ester‐directed acetoxylation, an enantioselective total synthesis of (−)‐spiroxins A and C and the first total synthesis of (−)‐spiroxin D have been achieved.