Bioinspired Total Synthesis of (±)-Antroalbocin A enabled by a Photochemical 1,3-Acyl Shift

Abstract

The first bioinspired and protecting group free total synthesis of the antibacterial sesquiterpenoid antroalbocin A has been achieved in five linear steps from a literature-known intermediate with an overall yield of 6.7%. An intramolecular Robinson annulation gave rapid access to the tricyclic enone as starting material for a photochemical domino process of deconjugation and sigmatropic 1,3 acyl shift. Herein we further describe studies towards the use of photolytic sigmatropic 1,3-acyl shifts in the synthesis of bridged terpenoid building blocks.