Substituent Effect versus AromaticityA Curious Case of Fulvene Derivatives

A computational study on amino- and nitro-substituted penta- and heptafulvenes reveals the interplay between the aromaticity and the substituent effect (SE). Ring substitution alone has little influence on the aromaticity, but in combination with an exo substituent of opposite properties, it substan...

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Bibliographic Details
Published in:Journal of organic chemistry 2023-10, Vol.88 (20), p.14775-14780
Main Authors: Wieczorkiewicz, Pawel A., Zborowski, Krzysztof K., Krygowski, Tadeusz M., Szatylowicz, Halina
Format: Article
Language:English
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Summary:A computational study on amino- and nitro-substituted penta- and heptafulvenes reveals the interplay between the aromaticity and the substituent effect (SE). Ring substitution alone has little influence on the aromaticity, but in combination with an exo substituent of opposite properties, it substantially enhances the cyclic π-electron delocalization. Despite the SE being stronger for β substitution, only γ substitution leads to higher aromaticity. An explanation is provided by the electron density of delocalized bonds (EDDB) method, which proves to be a valuable tool in analyzing both cyclic delocalization and the SE.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.3c01539