Asymmetric Total Synthesis of (+)-Bermudenynol, a C15 Laurencia Metabolite with a Vinyl Chloride Containing Oxocene Skeleton, through Intramolecular Amide Enolate Alkylation

A substrate-controlled asymmetric total synthesis of (+)-bermudenynol, a compact and synthetically challenging C(15)Laurencia metabolite that contains several halogen atoms, is reported. The oxocene core, which contains a vinyl chloride, was constructed by an efficient and highly stereoselective intramolecular amide enolate alkylation (IAEA). This result showcases the broad utility of the IAEA methodology as a useful alternative for cases in which the ring-closing metathesis is inefficient.