Enantioselective Total Synthesis and Determination of the Absolute Configuration of the 4,6,8,10,16,18-Hexamethyldocosane from Antitrogus parvulus

A copper‐catalyzed sp3–sp3 cross‐coupling for fragment coupling in a total synthesis is demonstrated. The diastereo‐ and enantioselective total synthesis of the 4,6,8,10,16,18‐hexamethyldocosanes highlights the synthetic power of deoxypropionate construction based on an ortho‐diphenylphosphanylbenzoyl (o‐DPPB)‐directed and copper‐mediated allylic substitution with Grignard reagents (see scheme).