Abstract
Barbaralanes and semibullvalenes are generally fluxional molecules renowned for their exceedingly low Cope rearrangement activation barriers and their close approach to homoaromaticity. The title compounds are unusual in that they do not undergo the Cope rearrangement and are locked as a single tautomer with no evidence whatsoever for the existence of the other “open” tautomer. This total lack of the Cope rearrangement was demonstrated through variable‐temperature 13C NMR spectroscopy and computational studies. Copyright © 2016 John Wiley & Sons, Ltd.
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