Asymmetric Total Syntheses of (+)-Davisinol and (+)-18-Benzoyldavisinol: A HAT-Initiated Transannular Redox Radical Approach

Kuan Yu; Fengjie Yao; Qingrui Zeng; Hujun Xie; Hanfeng Ding

doi:10.1021/jacs.1c05703

Asymmetric Total Syntheses of (+)-Davisinol and (+)-18-Benzoyldavisinol: A HAT-Initiated Transannular Redox Radical Approach

J Am Chem Soc. 2021 Jul 21;143(28):10576-10581. doi: 10.1021/jacs.1c05703. Epub 2021 Jul 9.

Authors

Kuan Yu¹, Fengjie Yao¹, Qingrui Zeng¹, Hujun Xie², Hanfeng Ding^{1

3}

Affiliations

¹ Department of Chemistry, Zhejiang University, Hangzhou 310058, China.
² Department of Applied Chemistry, Zhejiang Gongshang University, Hangzhou 310018, China.
³ State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China.

PMID: 34240855
DOI: 10.1021/jacs.1c05703

Abstract

The first and asymmetric total syntheses of two C11-oxygenated hetisine-type diterpenoid alkaloids, namely, (+)-davisinol and (+)-18-benzoyldavisinol, is described. The concise synthetic approach features a HAT-initiated transannular redox radical cyclization, an ODI-Diels-Alder cycloaddition, and an acylative kinetic resolution. By incorporating an efficient late-stage assembly of the azabicycle, our strategy would streamline the synthetic design of C₂₀-diterpenoid alkaloids and pave the way for their modular syntheses.

Publication types

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