Asymmetric Total Synthesis of Hasubanan Alkaloids: Periglaucines A-C, N,O-Dimethyloxostephine and Oxostephabenine

Shaolei Ding; Yingbo Shi; Baochao Yang; Min Hou; Haibing He; Shuanhu Gao

doi:10.1002/anie.202214873

Asymmetric Total Synthesis of Hasubanan Alkaloids: Periglaucines A-C, N,O-Dimethyloxostephine and Oxostephabenine

Angew Chem Int Ed Engl. 2023 Jan 9;62(2):e202214873. doi: 10.1002/anie.202214873. Epub 2022 Dec 2.

Authors

Shaolei Ding¹, Yingbo Shi², Baochao Yang¹, Min Hou¹, Haibing He³, Shuanhu Gao^{1

3}

Affiliations

¹ Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062, China.
² College of Chemistry and Materials Science, Sichuan Normal University, 5 Jingan Road, Chengdu, 610068, China.
³ Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062, China.

PMID: 36357322
DOI: 10.1002/anie.202214873

Abstract

We report herein the asymmetric total synthesis of periglaucines A-C, N,O-dimethyloxostephine and oxostephabenine. The key strategies used include: 1) a Rh^I -catalyzed regio- and diastereoselective Hayashi-Miyaura reaction to connect two necessary fragments; 2) an intramolecular photoenolization/Diels-Alder (PEDA) reaction to construct the highly functionalized tricyclic core skeleton bearing a quaternary center; 3) a bio-inspired intramolecular Michael addition and transannular acetalization to generate the aza[4.4.3]propellane and the tetrahydrofuran ring.

Keywords: Hasubanan Alkaloids; Natural Products; Photoenolization/Diels-Alder Reaction; Quaternary Centers; Total Synthesis.

Publication types

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

MeSH terms

Alkaloids*
Cycloaddition Reaction
Heterocyclic Compounds, 4 or More Rings
Stereoisomerism

Substances

hasubanan
Alkaloids
Heterocyclic Compounds, 4 or More Rings