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Expedient Synthesis of Fused Azepine Derivatives Using a Sequential Rhodium(II)‐Catalyzed Cyclopropanation/1‐Aza‐Cope Rearrangement of Dienyltriazoles
Author(s) -
Schultz Erica E.,
Lindsay Vincent N. G.,
Sarpong Richmond
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201405356
Subject(s) - cyclopropanation , carbenoid , rhodium , intramolecular force , azepine , chemistry , cope rearrangement , diene , catalysis , bicyclic molecule , combinatorial chemistry , sulfonyl , medicinal chemistry , stereochemistry , organic chemistry , natural rubber , alkyl
A general method for the formation of fused dihydroazepine derivatives from 1‐sulfonyl‐1,2,3‐triazoles bearing a tethered diene is reported. The process involves an intramolecular cyclopropanation of an α‐imino rhodium(II) carbenoid, leading to a transient 1‐imino‐2‐vinylcyclopropane intermediate which rapidly undergoes a 1‐aza‐Cope rearrangement to generate fused dihydroazepine derivatives in moderate to excellent yields. The reaction proceeds with similar efficiency on gram scale. The use of catalyst‐free conditions leads to the formation of a novel [4.4.0] bicyclic heterocycle.