Stereodivergent Total Syntheses of (+)-Mycaperoxides C, D, G Methyl Ester and (-)-Mycaperoxide B.
NMR analysis
endoperoxide
peroxycarbenium ion ions
ring-expansion
total synthesis
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783
Informations de publication
Date de publication:
27 Jan 2023
27 Jan 2023
Historique:
received:
26
09
2022
pubmed:
29
10
2022
medline:
1
2
2023
entrez:
28
10
2022
Statut:
ppublish
Résumé
Mycaperoxides are natural endoperoxides isolated from different Mycale genus sponges, showing significant antiviral or antibacterial activities. We report herein the first total syntheses of representative congeners of this family from sclareol using a stereodivergent approach. Thus, an innovative oxidative ring expansion of cyclobutanol was used to bring the 1,2-dioxane subunit, and a Mukaiyama aldol reaction on peroxycarbenium species was utilized to install the propionic acid subunit. During the study toward (+)-mycaperoxide D methyl ester (2), the isolation of the eight possible diastereomers under their ethyl thioester form allowed to build a pertinent database for further NMR assignment studies. Thus, we completed the total syntheses of (+)-mycaperoxides D, C, G methyl ester, and (-)-mycaperoxide B in 11 to 15 steps, confirming their original assignment.
Identifiants
pubmed: 36305658
doi: 10.1002/chem.202203004
pmc: PMC10107902
doi:
Substances chimiques
Esters
0
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202203004Subventions
Organisme : Centre National de la Recherche Scientifique
ID : MYCOXY
Informations de copyright
© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
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