Asymmetric Total Synthesis of Hasubanan Alkaloids: Periglaucines A–C, N, O‐Dimethyloxostephine and Oxostephabenine. (2nd December 2022)

• Record Type: Journal Article
• Authors: Ding, Shaolei; Shi, Yingbo; Yang, Baochao; Hou, Min; He, Haibing; Gao, Shuanhu
• Is Part Of: Angewandte Chemie. Volume 135:Number 2(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-12-02
• Subjects: Hasubanan Alkaloids -- Natural Products -- Photoenolization/Diels–Alder Reaction -- Quaternary Centers -- Total Synthesis; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202214873
• Languages: English
• ISSNs: 0044-8249

Abstract

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. Abstract : Asymmetric total synthesis of the hasubanan alkaloids periglaucines A–C, N, O ‐dimethyloxostephine and oxostephabenine is described. The key strategies include: 1) a Rh I ‐catalyzed regio‐ and diastereoselective Hayashi‐Miyaura reaction; 2) an intramolecular photoenolization/Diels–Alder (PEDA) reaction; and 3) bio‐inspired intramolecular Michael addition and transannular acetalization.