Total Synthesis of (+)-γ-Lycorane

Significance

Ojima and co-workers report a short and efficient total synthesis of (+)-γ-Lyco­rane (41% yield, 6 steps). The focal points of the synthesis are (a) the desymmetrization of a cis-1,4-dibenzoyloxycyclohex-2-ene via a Pd-catalyzed asymmetric allylic alkylation with a novel chiral biphenol-based monodentate phosphor­amidite ligand and (b) a diastereoselective Pd-catalyzed allylic amination-intramolecular Heck reaction cascade to construct the pentacyclic core of the natural product.