A Synthesis of (±)‐Aplydactone. Issue 37 (30th June 2016)

• Record Type: Journal Article
• Authors: Meier, Robin; Trauner, Dirk
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 37(2016)
• Page Start: 11251
• Page End: 11255
• Publication Date: 2016-06-30
• Subjects: cycloaddition -- halogenation -- natural products -- photochemistry -- radical reactions; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201604102
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Aplydactone is an unusual brominated sesquiterpenoid isolated from the sea hare Aplysia dactylomela . Its highly strained skeleton contains two four‐ and three six‐membered rings and features three adjacent quaternary carbon atoms. Although it is most likely of photochemical origin, attempts to generate it from a chamigrane precursor have failed thus far. In this work, we present a total synthesis of aplydactone that relies on two photochemical key steps that are not biomimetic but highly effective in establishing the two cyclobutane rings. Our synthesis also features an unusual Barbier‐type cyclization and culminates in new radical conditions to install the sterically hindered secondary bromide of the natural product. Abstract : The unusual sesquiterpenoid aplydactone was obtained by total synthesis. The core skeleton was constructed by two non‐biomimetic photochemical reactions, a diastereoselective [2+2] cycloaddition, a photochemical Wolff rearrangement, and a Barbier reaction. New radical conditions were developed for installing the sterically hindered secondary bromide.