Synthetic Strategy for Construction of Highly Congested Tetracyclic Core (6-5-7-4) of Harziane Diterpenoids

Org Lett. 2021 Jun 4;23(11):4088-4093. doi: 10.1021/acs.orglett.1c00769. Epub 2021 May 14.

Abstract

The structurally intriguing tetracyclic core of complex harziane diterpenoid was constructed in 14 steps from commercially available 3-ethoxycyclohex-2-en-1-one. The key steps were a Mn/Cu-mediated oxidative 1,3-dicarbonyl radical cascade cyclization reaction, which diastereoselectively formed the core of dimethylbicyclo[3.2.1]octane structure, and a Au-catalyzed diastereoselective formal [2 + 2] cycloaddition for construction of the harziane diterpenoid tetracyclic framework. The developed method paves the way for achieving total synthesis of this type of complex natural product.

Publication types

  • Research Support, Non-U.S. Gov't