Selective preparative ‘oxidase phase’ in sesquiterpenoids: the radical approach

Abstract

The necessity for highly selective oxidative transformations towards the synthesis of complex natural compounds such as sesquiterpenoids makes total synthesis a rich terrain of development for powerful widely applicable methods. Due to excessive oxidative decoration of sesquiterpenoids, which is traced back to the impressive performance of monooxygenases, synthetic efforts have been recently directed also towards more monooxygenase-like radical approaches to address the synthetic challenge of installing an ‘oxidase phase’ in their carbocycles. This review collects recent total syntheses of sesquiterpenoids relying mainly on radical reactions for allylic hydroxylations, hydrations and C-H oxidations.