Intramolecular conjugate displacement (ICD) reactions, developed by the Clive group, form carbocycles and polycyclic amines by intramolecular nucleophilic attack on a Michael acceptor with an allylic leaving group. Quantum mechanical investigations with density functional theory show that ICDs involve a stepwise addition, forming an intermediate stabilized carbanion, followed by elimination. The electron-withdrawing nature of the allylic leaving group facilitates the addition by negative hyperconjugation; the twist-boat conformation of the addition and intermediate is stabilized by this interaction. In the absence of an activating electron-withdrawing group as part of the Michael acceptor, a high energy concerted SN2' reaction occurs. The reactions of carbon nucleophiles have lower activation energies than those of amines.
1‐Adamantanol (I) wird in den Carbazinsäureester (II) übergeführt, der mit N‐Brom‐ oder N‐Jod‐succinimid in Methylenchlorid bei Raumtemperatur 1‐ Brom‐ (IIIa) bzw. 1‐Jodadamantan (IIIb) liefert.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.