Bioinspired Total Synthesis of Cephalotaxus Diterpenoids and Their Structural Analogues

Herein, we present a unified chemical synthesis of three subgroups of cephalotaxus diterpenoids. Key to the success lies in adopting a synthetic strategy that is inspired by biosynthesis but is opposite in nature. By employing selective one‐carbon introduction and ring expansion operations, we have...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2024-05, Vol.63 (22), p.e202402931-n/a
Main Authors: Shao, Hui, Ma, Zhi‐Hua, Cheng, Yang‐Yang, Guo, Xiao‐Feng, Sun, Ya‐Kui, Liu, Wen‐Jie, Zhao, Yu‐Ming
Format: Article
Language:English
Subjects:
Asymmetry
Biosynthesis
Cephalotaxus - chemistry
cephalotaxus diterpenoids
Chemical synthesis
Diterpenes
Diterpenes - chemical synthesis
Diterpenes - chemistry
Enantiomers
Esters
Intermediates
Michael reaction
Molecular Structure
Nucleotide sequence
radical cyclization
ring expansion
Stereoisomerism
Subgroups
total synthesis
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Summary:Herein, we present a unified chemical synthesis of three subgroups of cephalotaxus diterpenoids. Key to the success lies in adopting a synthetic strategy that is inspired by biosynthesis but is opposite in nature. By employing selective one‐carbon introduction and ring expansion operations, we have successfully converted cephalotane‐type C18 dinorditerpenoids (using cephanolide B as a starting material) into troponoid‐type C19 norditerpenoids and intact cephalotane‐type C20 diterpenoids. This synthetic approach has enabled us to synthesize cephinoid H, 13‐oxo‐cephinoid H, 7‐oxo‐cephinoid H, fortalpinoid C, 7‐epi‐fortalpinoid C, cephanolide E, and 13‐epi‐cephanolide E. Furthermore, through the development of an intermolecular asymmetric Michael reaction between β‐oxo esters and β‐substituted enones, we have achieved the enantioselective synthesis of advanced intermediates within our synthetic sequence, thus formally realizing the asymmetric total synthesis of the cephalotaxus diterpenoids family. A unified synthetic approach inspired by biosynthesis is presented for producing three subgroups of cephalotaxus diterpenoids. By selectively introducing carbon atoms and expanding rings, cephalotane‐type C18 dinorditerpenoids can be transformed into troponoid‐type C19 norditerpenoids and intact cephalotane‐type C20 diterpenoids. Several natural products, including fortalpinoid C and cephanolide E, were successfully synthesized.
ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202402931