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Dienamine‐Induced Divinylcyclopropane–Cycloheptadiene Rearrangements
Author(s) -
Apel Caroline,
Hartmann Sven Sören,
Lentz Dieter,
Christmann Mathias
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201813880
Subject(s) - pericyclic reaction , sigmatropic reaction , chemistry , cycloaddition , cope rearrangement , stereospecificity , organocatalysis , amine gas treating , catalysis , reactive intermediate , stereochemistry , enantioselective synthesis , organic chemistry
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 situ‐generated divinylcyclopropanes. The reactive motif was generated by condensation of 4‐(2‐vinylcyclopropyl)but‐2‐enal derivatives with a secondary amine catalyst to form a transient dienamine. The cycloheptadiene products could be obtained in high yield and excellent diastereoselectivity. Importantly, the reaction was demonstrated to be stereospecific, proceeding under mild conditions, while exhibiting broad functional group tolerance.