Total Synthesis of Illisimonin A and Merrilactone A

Illicium sesquiterpenes are a large family of biologically active secondary metabolites isolated from Illicium species of plants and are well‐known for their activity of neurite outgrowth in cultured neurons. Herein, we propose a comprehensive biosynthetic pathway for illicium sesquiterpenes and rep...

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Published in:Angewandte Chemie International Edition 2023-08, Vol.62 (31), p.e202306367-n/a
Main Authors: Gong, Xu, Huang, Juan, Sun, Xiangrui, Chen, Ziling, Yang, Ming
Format: Article
Language:English
Subjects:
Aldehydes
Axonogenesis
Biological activity
Desymmetrization
Illicium
Illicium Sesquiterpenes
Lactones
Metabolites
Molecular Structure
Natural Product Synthesis
Neurons
Oxidation
Phosphine
Phosphines
Plant species
Reductive Heck Reaction
Retro-Dieckmann Condensation
Secondary metabolites
Sesquiterpenes
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Summary:Illicium sesquiterpenes are a large family of biologically active secondary metabolites isolated from Illicium species of plants and are well‐known for their activity of neurite outgrowth in cultured neurons. Herein, we propose a comprehensive biosynthetic pathway for illicium sesquiterpenes and report a synthetic route to illisimonin A and merrilactone A based on it. We think that the carbon scaffolds of most of the illicium sesquiterpenes could be synthesized from a dicarbonyl derivative of allo‐cedrane through retro‐Dieckmann condensation, oxidative cleavage and aldol reaction at suitable oxidation states in Nature. The common intermediate for illisimonin A and merrilactone A similar to the dicarbonyl derivative of allo‐cedrane was assembled with up to 82 % ee by an asymmetric intramolecular desymmetrizing reductive Heck reaction by the use of a new type of chiral phosphine ligand. The syntheses of illisimonin A and merrilactone A supported the key transformations of the proposed biosynthetic pathway. A comprehensive biosynthetic pathway was proposed for illicium sesquiterpenes. The key transformations of the biosynthetic pathway, which include retro‐Dieckmann condensation, oxidative cleavage and aldol reaction, were supported by the total syntheses of illisimonin A and merrilactone A from a common intermediate.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202306367