One-Pot Synthesis of Metastable 2,5-Dihydrooxepines through Retro-Claisen Rearrangements: Method and Applications.
2,5-dihydrooxepines
density functional calculations
herbicides
sigmatropic rearrangement
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:
26 Jun 2019
26 Jun 2019
Historique:
received:
10
04
2019
pubmed:
30
4
2019
medline:
30
4
2019
entrez:
30
4
2019
Statut:
ppublish
Résumé
A one-pot methodology to synthesize metastable bicyclic 2,5-dihydrooxepines from cyclic 1,3-diketones and 1,4-dibromo-2-butenes through the retro-Claisen rearrangement of syn-2-vinylcyclopropyl diketone intermediates is reported. DFT calculations were performed to understand the reaction selectivity and mechanisms towards [1,3]- or [3,3]-sigmatropic rearrangements, highlighting the crucial influence of the temperature. The reaction was successfully applied to a short protecting group-free total synthesis of radulanin A, a natural 2,5-dihydrobenzoxepine. Moreover, the strong herbicidal potential of this natural product is demonstrated for the first time.
Identifiants
pubmed: 31033060
doi: 10.1002/chem.201901675
doi:
Types de publication
Journal Article
Langues
eng
Pagination
8643-8648Subventions
Organisme : École Polytechnique, Université Paris-Saclay
Organisme : Université Pierre et Marie Curie
Organisme : Centre National de la Recherche Scientifique
Informations de copyright
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.