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Cover Feature: Dual Activation of Aromatic Diels–Alder Reactions (Chem. Eur. J. 42/2019)
Author(s) -
Narsaria Ayush K.,
Hamlin Trevor A.,
Lammertsma Koop,
Bickelhaupt F. Matthias
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201902538
Subject(s) - cycloaddition , diels–alder reaction , reactivity (psychology) , ring strain , chemistry , benzene , diene , heteroatom , ring (chemistry) , aromaticity , distortion (music) , homo/lumo , computational chemistry , photochemistry , stereochemistry , materials science , organic chemistry , molecule , catalysis , medicine , amplifier , natural rubber , alternative medicine , optoelectronics , cmos , pathology
The Diels–Alder cycloaddition of benzene requires harsh reaction conditions, whereas their bent cyclophane analogs react smoothly under mild conditions. Through state‐of‐the‐art quantum chemical calculations, this work has pinpointed the enhanced reactivity of cyclophanes to the (i) pre‐distortion of the aromatic core resulting in a reduced activation strain and/or (ii) enhanced interaction with the dienophile through a distortion‐controlled lowering of the HOMO–LUMO gap within the diene. These results demonstrate how the Diels–Alder reactivity can be tuned by different modes of geometrical distortion (meta‐ versus para‐bridging) and by heteroatom substitution in the aromatic ring. More information can be found in the Full Paper by T. A. Hamlin, K. Lammertsma, F. M. Bickelhaupt, et al. on page 9902.