DFT Insights into Superelectrophilic Activation of α,β-Unsaturated Nitriles and Ketones in Superacids Full article
| Journal |
Organic and Biomolecular Chemistry
ISSN: 1477-0520 , E-ISSN: 1477-0539 |
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| Output data | Year: 2022, Volume: 20, Number: 34, Pages: 6799-6808 Pages count : 10 DOI: 10.1039/d2ob01141g | ||||
| Tags | N-ARYL AMIDES; CATALYZED-REACTIONS; INTRAMOLECULAR CYCLIZATION; AROMATIC-COMPOUNDS; CARBONYL-COMPOUNDS; HOUBEN-HOESCHH-ZEOLITE; ACIDS; 1-PHENYL-2-PROPEN-1-ONES; CHLOROALUMINATE | ||||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | Ministry of Science and Higher Education of the Russian Federation | 0239-2021-0009 |
| 2 | Ministry of Science and Higher Education of the Russian Federation | 0238-2021-0007 (АААА-А21-121011490019-9) |
Abstract:
Superelectrophilic activation of α,β-unsaturated carbonyl compounds and their isoelectronic analogs, proceeding normally under superacidic conditions, have led to a great variety of beneficial synthetic transformations. However, the essence of such activation is not yet fully recognized, while a number of alternative views on the subject have been discussed at length in the literature. Here, taking the example of virtual reactions of cinnamonitrile and benzalacetone with benzene, their feasible mechanistic variants, including multiple protonation (coordination to AlCl3) of the reactants, were analyzed based on density functional theory (DFT). It is revealed that the most plausible reaction pathways involve the initial N- or O-protonation (coordination to AlCl3) of the activated compounds followed by subsequent protonation on the α-C-atom. Dicationic superelectrophiles thus formed ensure practically barrier-free reactions with benzene in addition to a more favorable energetic profile of their generating, which is in marked contrast to other potential reaction pathways.
Cite:
Genaev A.M.
, Salnikov G.E.
, Koltunov K.Y.
DFT Insights into Superelectrophilic Activation of α,β-Unsaturated Nitriles and Ketones in Superacids
Organic and Biomolecular Chemistry. 2022. V.20. N34. P.6799-6808. DOI: 10.1039/d2ob01141g WOS Scopus РИНЦ ANCAN PMID OpenAlex
DFT Insights into Superelectrophilic Activation of α,β-Unsaturated Nitriles and Ketones in Superacids
Organic and Biomolecular Chemistry. 2022. V.20. N34. P.6799-6808. DOI: 10.1039/d2ob01141g WOS Scopus РИНЦ ANCAN PMID OpenAlex
Dates:
| Submitted: | Jun 24, 2022 |
| Accepted: | Aug 3, 2022 |
| Published online: | Aug 6, 2022 |
| Published print: | Sep 1, 2022 |
Identifiers:
| Web of science: | WOS:000839581200001 |
| Scopus: | 2-s2.0-85136317992 |
| Elibrary: | 50357031 |
| Chemical Abstracts: | 2022:2116738 |
| Chemical Abstracts (print): | 180:11595 |
| PMID: | 35959855 |
| OpenAlex: | W4290000641 |