An Efficient One‐Pot Approach to Bridged Bicyclic Ring‐Systems through Consecutive Hetero‐Domino Transformations: A Mechanistic Rationale and Further Rearrangements

This article describes the design of olefin-generated/reagent-modulated consecutive hetero-domino reactions of 1,2-unsaturated bicyclic diols, which are potentially of great use, initiated by PhI(OAc) 2 , continued by [Ph(OAc) 4 ], and completed by use of a mild base (K 2 CO 3 ). Inversion of a quaternary center has been achieved through a three-reaction sequence: a domino transformation followed by an m-CPBA-mediated Baeyer- Villiger oxidation and subsequent reductive lactone ring opening.