Formal Synthesis of (±)-Coriolin by Diastereocontrolled Nickel(0)-Catalyzed 'Metallo-ene-type' Cyclization/Methoxycarbonylation

Abstract

Bicyclooctanone (±)-2, an advanced intermediate for the synthesis of (±)-coriolin, has been synthesized in ten steps starting from 2,2-dimethylpent-4-enal (7). The key step 6 → 3 + 11 is a highly diastereoselective, Ni⁰-catalyzed, tandem intramolecular alkene allylation/carbonylation reaction.