Ring Enlargement of Three-Membered Heterocycles by Treatment with In Situ Formed Tricyanomethane.
cyanoform
nitrogen heterocycles
reaction mechanisms
reactive intermediates
ring expansion
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783
Informations de publication
Date de publication:
15 May 2020
15 May 2020
Historique:
received:
08
01
2020
pubmed:
29
1
2020
medline:
29
1
2020
entrez:
29
1
2020
Statut:
ppublish
Résumé
Although the chemistry of elusive tricyanomethane (cyanoform) has been studied during a period of more than 150 years, this compound has very rarely been utilized in the synthesis or modification of heterocycles. Three-membered heterocycles, such as epoxides, thiirane, aziridines, or 2H-azirines, are now treated with tricyanomethane, which is generated in situ by heating azidomethylidene-malonodinitrile in tetrahydrofuran at 45 °C or by adding sulfuric acid to potassium tricyanomethanide. This leads to ring expansion with formation of 2-(dicyanomethylidene)oxazolidine derivatives or creation of the corresponding thiazolidine, imidazolidine, or imidazoline compounds and opens up a new access to these push-pull-substituted olefinic products. The regio- and stereochemistry of the ring-enlargement processes are discussed, and the proposed reaction mechanisms were confirmed by using
Identifiants
pubmed: 31990418
doi: 10.1002/chem.202000089
pmc: PMC7318174
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
6158-6164Subventions
Organisme : Verband der Chemischen Industrie
Organisme : Deutscher Akademischer Austauschdienst
ID : A/11/74615
Informations de copyright
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
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