Rapid formation of hindered cores using an oxidative Prins process.

An unprecedented oxidative Prins transformation on phenol derivatives mediated by a hypervalent iodine reagent has been developed. This method allows a rapid access to highly substituted compact systems present in several natural products via a carbon-based addition on an aromatic core. Substitution at each ring position has been demonstrated, enabling synthesis of molecules with up to two contiguous quaternary carbon centers in good yield.

An unprecedented oxidative Wagner-Meerwein transposition.

An oxidative Wagner-Meerwein transposition involving different functionalities mediated by a hypervalent iodine reagent has been accomplished. The strategy fits within the concept of "aromatic ring umpolung" and allows rapid access to highly functionalized cores.