Asymmetric synthesis of venezuelaene's core with a trans-fused [5-5] ring system

Abstract

Herein, we report the asymmetric synthesis of venezuelaene's tetracyclic core, featuring a diastereoselective IMDA to construct the [6-5-6-7] skeleton, followed by stereoselective Simmons–Smith reaction, cyclopropane ring-opening, and Wolff rearrangement to install the challenging trans-fused [5-5] ring system.