Differential Effects of Nitrogen-Substitution in 5- and 6-Membered Aromatic Motifs
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nihms-1598257.pdf
Description
Accepted version
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1.46 MB
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Author(s)
Levandowski, Brian
Abularrage, Nile S
Raines, Ronald T
Alternative Title
Differential Effects of Nitrogen Substitution in 5‐ and 6‐Membered Aromatic Motifs
Date Issued
March 2020
Journal
Chemistry
Publisher
Wiley
Citation
Levandowski, Brian J. et al., "Differential Effects of Nitrogen Substitution in 5‐ and 6‐Membered Aromatic Motifs." Chemistry 26, 41 (July 2020): 8862-66 ©2020 Authors
Version
Author's final manuscript
Abstract
The replacement of carbon with nitrogen can affect the aromaticity of organic rings. Nucleus-independent chemical shift (NICS) calculations at the center of the aromatic π-systems reveal that incorporating nitrogen into 5-membered heteroaromatic dienes has only a small influence on aromaticity. In contrast, each nitrogen incorporated into benzene results in a sequential and substantial loss of aromaticity. The contrasting effects of nitrogen substitution in 5-membered dienes and benzene are reflected in their Diels–Alder reactivities as dienes. 1,2-Diazine experiences a 1011-fold increase in reactivity upon nitrogen substitution at the 4- and 5-positions, whereas a 5-membered heteroaromatic diene, furan, experiences a comparatively incidental 102-fold increase in reactivity upon nitrogen substitution at the 3- and 4-positions. ©2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Creative Commons Attribution-Noncommercial-Share Alike
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DOI of Published Version
https://doi.org/10.1002/CHEM.202000825
