2021
DOI: 10.3390/org2010003
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Application of β-Phosphorylated Nitroethenes in [3+2] Cycloaddition Reactions Involving Benzonitrile N-Oxide in the Light of a DFT Computational Study

Abstract: The regiochemistry of [3+2] cycloaddition (32CA) processes between benzonitrile N-oxide 1 and β-phosphorylated analogues of nitroethenes 2a–c has been studied using the Density Functional Theory (DFT) at the M062X/6-31+G(d) theory level. The obtained results of reactivity indices show that benzonitrile N-oxide 1 can be classified both as a moderate electrophile and moderate nucleophile, while β-phosphorylated analogues of nitroethenes 2a–c can be classified as strong electrophiles and marginal nucleophiles. Mo… Show more

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Cited by 22 publications
(15 citation statements)
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“…The polar character of these zw-type 32CA reactions was evaluated by computing the global electron density transfer (GEDT) [52,53] at the TSs. The GEDT values in THF range by between 0.11 and 0.15 e. These values indicate that the corresponding zw-type 32CA reactions have somewhat polar character.…”
Section: Analysis Of the Cdft Reactivity Indices Of The Reagentsmentioning
confidence: 99%
See 1 more Smart Citation
“…The polar character of these zw-type 32CA reactions was evaluated by computing the global electron density transfer (GEDT) [52,53] at the TSs. The GEDT values in THF range by between 0.11 and 0.15 e. These values indicate that the corresponding zw-type 32CA reactions have somewhat polar character.…”
Section: Analysis Of the Cdft Reactivity Indices Of The Reagentsmentioning
confidence: 99%
“…The Bonding Evolution Theory (BET) [54], which combines the topological analysis of the ELF with catastrophes theory [54], allows characterizing the electron density rearrangement along a reaction path and, thus, enables a description of the bonding changes associated with a given molecular mechanism [55,56]. The molecular mechanism of zw-type 32CA reactions involving NOs and different types of ethylene derivatives has already been recently studied [2,9,10,12,53,[57][58][59][60][61]. As a general outlook, these reactions start with the depopulation of the C≡N triple bond of the NO framework and the C=C double bond of the ethylene derivative, which gives rise to the creation of the corresponding carbon pseudoradical centers [62].…”
Section: Characterization Of the Bond Formation Processmentioning
confidence: 99%
“…Additionally, the unsaturated nitroalkyne and nitro−ethyl ester are fixed in their conformation, thereby limiting the reaction of the double bond to a single side. Moreover, the reaction course is determined by the attack on the electrophically activated β−position of nitroethene [39,40]. Therefore, we predicted the TS of the re or si face of the unsaturated nitroalkyne as in the TS in Figure 4.…”
Section: Resultsmentioning
confidence: 99%
“…This analysis was performed based on CDFT reactivity indices ( Table 1 ) [ 34 ]. A similar approach was recently used to explain the course of many different types of cycloaddition processes [ 35 , 36 , 37 , 38 ]. It was found that nitrones 1 exhibited a moderately electrophilic nature.…”
Section: Resultsmentioning
confidence: 99%