The change of aromaticity along a Diels-Alder reaction path.
[reaction: see text] Quinodimethanes are highly reactive toward dienophiles since Diels-Alder cycloaddition results in an aromatic product. Density functional-based (13)C, (1)H NMR, NICS, and MO-NICS calculations indicate that the increase of aromatic character of the developing benzenoid ring along the reaction path is especially pronounced after the transition state is reached, even though the number of pi orbitals decreases. The forming aliphatic ring exhibits large ring current effects during the reaction.
Corminboeuf
Clémence
C
Department of Physical Chemistry, University of Geneva, 30 quai Ernest-Ansermet, CH-1211 Genève 4, Switzerland. clemence.corminboeuf@chiphy.unige.ch
Heine
Thomas
T
Weber
Jacques
J