Participation of phosphorylated analogues of nitroethene in Diels–Alder reactions with anthracene: a molecular electron density theory study and mechanistic aspect
Authors:
- Agnieszka Kącka-Zych
Abstract
The structure and the contribution of the bis(2-chloroethyl) 2-nitro 1a and 2-bromo2-nitroethenylphosphonates 1b with anthracene 2 in the Diels–Alder (DA) reactions have been studied within the Molecular Electron Density Theory (MEDT) at the B3LYP functional together with 6-31G(d), 6-31+G(d) and 6-31+G(d,p) basic sets. Analysis of the Conceptual Density Functional Theory (CDFT) reactivity indices indicates that 1a and 1b can be classified as a strong electrophile and marginal nucleophile, while 2 is classified as a strong electrophile and strong nucleophile. The studied DA reactions take place through a one-step mechanism. A Bonding Evolution Theory (BET) of the one path associated with the DA reaction of 1a with 2 indicates that it is associated with non-concerted two-stage one-step mechanism. BET analysis shows that the first C2-C3 single bond is formed in Phase VI, while the second C1-C6 single bond is formed in the Phase VIII. The formation of both single bonds occurs through the merging of two C2 and C3, C1 and C6 pseudoradical centers, respectively.
- Record ID
- CUTb2615e0e3f50428988118a7b03386ff0
- Publication categories
- ;
- Author
- Journal series
- Organics , ISSN , e-ISSN 2673-401X, Annual
- Issue year
- 2020
- Vol
- 1
- No
- 1
- Pages
- 36-48
- Other elements of collation
- schem.; tab.; Bibliografia (na s.) - 46-48; Bibliografia (liczba pozycji) - 42; Oznaczenie streszczenia - Abstr.; Numeracja w czasopiśmie - Vol. 1, Iss. 1, Spec. Iss.
- Substantive notes
- Special Issue: Cycloaddition Reaction in Organic Synthesis
- Keywords in English
- diels–alder reaction, anthracene, molecular mechanism, bonding evolution theory, molecular electron density theory
- DOI
- DOI:10.3390/org1010004 Opening in a new tab
- URL
- https://www.mdpi.com/2673-401X/1/1/4 Opening in a new tab
- Language
- eng (en) English
- License
- Score (nominal)
- 5
- Uniform Resource Identifier
- https://cris.pk.edu.pl/info/article/CUTb2615e0e3f50428988118a7b03386ff0/
- URN
urn:pkr-prod:CUTb2615e0e3f50428988118a7b03386ff0
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