Understanding the molecular mechanism of the stereoselective conversion of N-trialkylsilyloxy nitronates into bicyclic isoxazoline derivatives
Authors:
- Agnieszka Kącka-Zych,
- Radomir Jasiński
Abstract
The conversion of N-trialkylsilyloxy nitronates into bicyclic isoxazoline derivatives has been explored using the density functional theory (DFT) method within the context of molecular electron density theory (MEDT) at the ωB97XD(PCM)/6-311G(d,p) theoretical level. The obtained results clearly indicated that this reaction proceeds via a domino process, including two pseudocyclic elemental reactions: nitronate-[3+2] cycloaddition and the elimination of trimethylsilanol. An exploration of the electron localization function (ELF) of the most significant points located along the intrinsic reaction coordinate (IRC) profile elucidates the molecular mechanism of the studied reactions. The bonding electron density changes along the reaction paths reveal that the analysed reactions take place via an asynchronous one-step mechanism. The first reaction of the domino process is characterized by six different phases associated with the formation of two C–C and C–O single bonds, while there are five different topological phases related to the formation of one O–H single bond and one N=C double bond in the second reaction of this domino process.
- Record ID
- CUT18a463a850654f37a2ccd3d65c6d1077
- Publication categories
- ;
- Author
- Journal series
- New Journal of Chemistry, ISSN 1144-0546, e-ISSN 1369-9261
- Issue year
- 2021
- Vol
- 45
- No
- 21
- Pages
- 9491-9500
- Other elements of collation
- rys.; schem.; tab.; wykr.; Bibliografia (na s.) - 9499-9500; Bibliografia (liczba pozycji) - 54; Oznaczenie streszczenia - Streszcz. ang.; Numeracja w czasopiśmie - Vol. 45, Iss. 21
- Substantive notes
- Electronic supplementary information (ESI) available [pdf].
- Keywords in English
- intramolecular [3+2] cycloaddition, 2-isoxazoline, nitrile N-oxide, molecular mechanism, molecular electron density theory
- DOI
- DOI:10.1039/d1nj01198g Opening in a new tab
- URL
- https://pubs.rsc.org/en/Content/ArticleLanding/2021/NJ/D1NJ01198G#!divAbstract Opening in a new tab
- Language
- eng (en) English
- Score (nominal)
- 70
- Additional fields
- Indeksowana w: Web of Science
- Uniform Resource Identifier
- https://cris.pk.edu.pl/info/article/CUT18a463a850654f37a2ccd3d65c6d1077/
- URN
urn:pkr-prod:CUT18a463a850654f37a2ccd3d65c6d1077
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