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submitted on 05.12.2018 and posted on 06.12.2018by Caroline Apel, Sven Sören Hartmann, Dieter Lentz, Mathias Christmann
Sigmatropic rearrangements constitute an important group
of pericyclic reactions. In contrast to cycloaddition reactions,
examples of catalytic variants of electrocyclic reactions and sigmatropic
rearrangements are still scarce in the chemical literature. Herein,
we report the first organocatalytic Cope rearrangement of in situgenerated
divinylcyclopropanes. The reactive motif is generated by
condensation of 4-(2-vinylcyclopropyl)but-2-enal derivatives and a
secondary amine catalyst to form a transient dienamine. The
cycloheptadiene products can be obtained in high yield and excellent
diastereoselectivity. Importantly, the reaction was demonstrated to be
stereospecific, proceeds under mild conditions, and shows broad
functional group tolerance.