Reductive Radical Annulation Strategy toward Bicyclo[3.2.1]octanes: Synthesis of ent-Kaurane and Beyerane Diterpenoids

Junming Zhuo; Chunlin Zhu; Jinbao Wu; Zijian Li; Chao Li

doi:10.1021/jacs.1c11623

Reductive Radical Annulation Strategy toward Bicyclo[3.2.1]octanes: Synthesis of ent-Kaurane and Beyerane Diterpenoids

J Am Chem Soc. 2022 Jan 12;144(1):99-105. doi: 10.1021/jacs.1c11623. Epub 2021 Dec 27.

Authors

Junming Zhuo^{1

2}, Chunlin Zhu^{1

2}, Jinbao Wu², Zijian Li², Chao Li^{1

2

3}

Affiliations

¹ Graduate School of Peking Union Medical College and Chinese Academy of Medical Sciences, Beijing 100730, China.
² National Institute of Biological Sciences, Beijing 102206, China.
³ Tsinghua Institute of Multidisciplinary Biomedical Research, Tsinghua University, Beijing 100084, China.

PMID: 34958563
DOI: 10.1021/jacs.1c11623

Abstract

Here we report a general [3 + 2] radical annulation that allows the facile construction of bicyclo[3.2.1]octane motifs in ent-kaurane- and beyerane-type diterpenoids. This radical annulation is difficult to control but was realized by harnessing an unprecedented and counterintuitive effect of TEMPO. Eleven natural products with a wide array of oxidation states are easily prepared, demonstrating the powerful utility of this straightforward synthetic strategy.

Publication types

Research Support, Non-U.S. Gov't