α-Ketol Rearrangement for Accessing Tetracyclic Natural Products

Tetracyclic natural products, which utilize the tetracycline skeleton, demonstrate a diverse array of biological activities. A critical structural feature of these compounds is the tertiary alcohol situated within a cis-decalin framework. In this study, we present a comprehensive protocol for the synthesis of tricyclic building blocks and complete carbon frameworks. This methodology facilitates the stereoselective synthesis of a specific enantiomer as well as its inversion to the corresponding opposite isomer via a ketol rearrangement.