Asymmetric Total Synthesis of Natural Lindenane Sesquiterpenoid Oligomers via a Triene as a Potential Biosynthetic Intermediate. (1st June 2022)

• Record Type: Journal Article
• Authors: Huang, Zhengsong; Huang, Ganxing; Wang, Xiao; Qin, Song; Fu, Shaomin; Liu, Bo
• Is Part Of: Angewandte Chemie. Volume 134:Number 29(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-06-01
• Subjects: Asymmetric Synthesis -- Oligomers -- Sesquiterpenoids -- Total Synthesis; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202204303
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A previously proposed triene of the lindenane skeleton was synthesized, characterized, and identified as the common intermediate for the non‐enzymatic synthesis of natural lindenane oligomers through linear, [4+2]‐type and [6+6]‐type homo‐ and hetero‐ dimerization under simulated physiological conditions. As a result, the following six natural products were successfully synthesized through thermal head‐to‐head, head‐to‐tail, and head‐to‐back binding modes: shizukaols A and J, cycloshizukaol A, chlorahupetone F, chlotrichene B, and trishizukaol A. Abstract : A conjugated triene was evidenced as a universal synthetic and biosynthetic intermediate toward various natural lindenane oligomers under simulated physiological conditions with high stereoselectivity. The related oligomerization modes involve linear connection, head‐to‐head [4+2] cycloaddition, head‐to‐tail [4+2] cycloaddition, head‐to‐back [4+2] cycloaddition, and head‐to‐tail [6+6] cycloaddition.