Total Synthesis of (±)-Clavilactones A, B, and Proposed D through Iron-Catalyzed Carbonylation-Peroxidation of Olefin

Biologically significant clavilactones A, B, and the previously proposed D have been synthesized through iron‐catalyzed carbonylation–peroxidation of a 1,5‐diene. Three steps from aldehydes, alkenes, and tert‐butylhydroperoxide build up α,β‐epoxy‐γ‐butyrolactone skeleton as a key building block for synthesis of clavilactone family and its derivatives. Based on our results, the structure of the proposed clavilactone D is not correct and requires revision. A general, concise, and efficient approach for synthesis of clavilactones A, B, and D has been established. Three steps from aldehydes, 1,5‐dienes, and tBuOOH build up α,β‐epoxy‐γ‐butyrolactones (see scheme, left) as the key building blocks for synthesis of clavilactone family and its derivatives. From these results, the previously proposed clavilactone D structure requires revision.