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Synthesis of Benzazepinones via Intramolecular Cyclization Involving Ketene Iminium Intermediates
Author(s) -
Kolleth Amandine,
Dagoneau Dylan,
Quinodoz Pierre,
Lumbroso Alexandre,
Avanthay Mickael,
Catak Saron,
SulzerMossé Sarah,
De Mesmaeker Alain
Publication year - 2019
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.201900168
Subject(s) - iminium , chemistry , ketene , intramolecular force , amide , aniline , ring (chemistry) , combinatorial chemistry , intramolecular reaction , selectivity , hydrolysis , computational chemistry , stereochemistry , medicinal chemistry , organic chemistry , catalysis
Herein, we describe a very straightforward and metal free method for the synthesis of benzazepinones through an intramolecular cyclization. This involves an ortho ‐vinyl‐anilino‐amide as starting material which is converted to a keteniminium intermediate that spontaneously cyclize to form a 7‐membered ring iminium. Under slightly basic hydrolysis conditions, this latter is ultimately converted to the desired benzazepinone. Control experiments on the electron density of the nitrogen constituting the aniline were performed to support our proposed mechanism and rationalize the selectivity of the reaction.