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Modular Access to Eight‐Membered N‐Heterocycles by Directed Carbonylative C−C Bond Activation of Aminocyclopropanes
Author(s) -
Boyd Olivia,
Wang GangWei,
Sokolova Olga O.,
Calow Adam D. J.,
Bertrand Sophie M.,
Bower John F.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201910276
Subject(s) - cyclopropane , intramolecular force , nucleophile , chemistry , ring (chemistry) , aryl , stereochemistry , ring strain , carbonylation , combinatorial chemistry , catalysis , medicinal chemistry , carbon monoxide , organic chemistry , alkyl
Aminocyclopropanes equipped with pendant nucleophiles undergo carbonylative heterocyclization triggered by C−C bond activation to generate eight‐membered N‐heterocycles. In these processes, intramolecular “capture” of a rhodacyclopentanone intermediate by an aryl or N‐based nucleophile is followed by C−C or C−N bond‐forming “collapse” to the targets. These studies demonstrate how the combination of cyclopropane strain release and the templating effect of catalytically generated metallacycles can be harnessed to enable otherwise challenging medium ring closures.