Differential Effects of Nitrogen-Substitution in 5- and 6-Membered Aromatic Motifs
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 c...
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| Format: | Article |
| Language: | English |
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Wiley
2021
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| Online Access: | https://hdl.handle.net/1721.1/129937 |
| _version_ | 1811089422286848000 |
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| author | Levandowski, Brian Abularrage, Nile S Raines, Ronald T |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Levandowski, Brian Abularrage, Nile S Raines, Ronald T |
| author_sort | Levandowski, Brian |
| collection | MIT |
| description | 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 |
| first_indexed | 2024-09-23T14:18:55Z |
| format | Article |
| id | mit-1721.1/129937 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T14:18:55Z |
| publishDate | 2021 |
| publisher | Wiley |
| record_format | dspace |
| spelling | mit-1721.1/1299372022-09-29T08:39:23Z Differential Effects of Nitrogen-Substitution in 5- and 6-Membered Aromatic Motifs Differential Effects of Nitrogen Substitution in 5‐ and 6‐Membered Aromatic Motifs Levandowski, Brian Abularrage, Nile S Raines, Ronald T Massachusetts Institute of Technology. Department of Chemistry 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 NIH (F32 GM137543) NIH Grant (R01 GM044783) NSF Grant (ACI-1548562) 2021-02-19T22:57:35Z 2021-02-19T22:57:35Z 2020-03 2020-03 2020-09-18T15:06:16Z Article http://purl.org/eprint/type/JournalArticle 1521-3765 https://hdl.handle.net/1721.1/129937 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 en https://dx.doi.org/10.1002/CHEM.202000825 Chemistry Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Wiley PMC |
| spellingShingle | Levandowski, Brian Abularrage, Nile S Raines, Ronald T Differential Effects of Nitrogen-Substitution in 5- and 6-Membered Aromatic Motifs |
| title | Differential Effects of Nitrogen-Substitution in 5- and 6-Membered Aromatic Motifs |
| title_full | Differential Effects of Nitrogen-Substitution in 5- and 6-Membered Aromatic Motifs |
| title_fullStr | Differential Effects of Nitrogen-Substitution in 5- and 6-Membered Aromatic Motifs |
| title_full_unstemmed | Differential Effects of Nitrogen-Substitution in 5- and 6-Membered Aromatic Motifs |
| title_short | Differential Effects of Nitrogen-Substitution in 5- and 6-Membered Aromatic Motifs |
| title_sort | differential effects of nitrogen substitution in 5 and 6 membered aromatic motifs |
| url | https://hdl.handle.net/1721.1/129937 |
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