Divergent Photocyclization/1,4-Sigmatropic Rearrangements for the Synthesis of Sesquiterpenoid Derivatives.

ABSTRACT

Combined experimental and computational efforts have demonstrated the utility of divergent photocyclization/1,4-sigmatropic rearrangement reactions for developing a general strategy toward the synthesis of cubebane-, spiroaxane-, and guaiane-type sesquiterpenes and related analogues. The configuration of the bridgehead substituent, the choice of solvent, and the wavelength of irradiation all impact diastereoselectivity in this tandem reaction process.