First Synthesis of the Pyrano‐Naphthoquinone Lactone (–)‐Arizonin C1

Pyrano‐naphthoquinones fused to a γ‐lactone ring are structurally and biologically interesting natural products. We have accomplished an enantioselective synthesis of (–)‐arizonin C1 (2d) in nine steps. We employed the Sharpless dihydroxylation of β,γ‐unsaturated ester 9d as a highly enantioselective (>99 % ee) access to the γ‐lactone intermediate 7d. Oxa‐Pictet–Spengler cyclization, oxidation, and epimerization as expected led to the conversion of 7d into 2d. The pentasubstituted naphthalene precursor 14 of ester 9d was obtained by Dötz benzannulation.