Tandem C-H oxidation/cyclization/rearrangement and its application to asymmetric syntheses of (-)-brussonol and (-)-przewalskine E

Natural products are a vital source of lead compounds in drug discovery. Development of efficient tandem reactions to build useful compounds and apply them to the synthesis of natural products is not only a significant challenge but also an important goal for chemists. Here we describe a tandem C-H oxidation/cyclization/rearrangement of isochroman-derived allylic silylethers, promoted by DDQ and InCl3. This method allows the efficient construction of tricyclic benzoxa[3.2.1] octanes with a wide substrate scope. We employ this tandem reaction to achieve the asymmetric total syntheses of (-)-brussonol and (-)-przewalskine E.