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Nitroacetylene as dipolarophile in [2 + 3] cycloaddition reactions with allenyl-type three-atom components: DFT computational study.

Jasiński R - Monatsh. Chem. (2015)

Bottom Line: [2 + 3] Cycloaddition reactions of nitroacetylene with allenyl-type three-atom components take place according to the polar, but a one-step mechanism.Alternatively to cycloadducts, during the reaction between the aforementioned reagents, zwitterionic structures with "extended" conformation may be formally created.However, this route is supported by neither kinetic nor thermodynamic factors.

View Article: PubMed Central - PubMed

Affiliation: Institute of Organic Chemistry and Technology, Cracow University of Technology, Cracow, Poland.

ABSTRACT

Abstract: [2 + 3] Cycloaddition reactions of nitroacetylene with allenyl-type three-atom components take place according to the polar, but a one-step mechanism. Alternatively to cycloadducts, during the reaction between the aforementioned reagents, zwitterionic structures with "extended" conformation may be formally created. However, this route is supported by neither kinetic nor thermodynamic factors.

No MeSH data available.


Key structures for reaction between nitroacetylene (1) and benzonitrile N-oxide (2a) in toluene according to DFT calculations at B3LYP/6-31G(d) theory level
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Fig3: Key structures for reaction between nitroacetylene (1) and benzonitrile N-oxide (2a) in toluene according to DFT calculations at B3LYP/6-31G(d) theory level

Mentions: So, in the case of a reaction with benzonitrile N-oxide in toluene, the bond at the β carbon atom introduced from nitroacetylene always is more advanced at the TS (Fig. 3). Formation of bonds in the area of the less favoured energetically TSB takes place in a more asynchronous manner (∆l > 0.2). Both TSs have a polar nature, which is reflected in the value of GEDT index (see Table 2).Fig. 3


Nitroacetylene as dipolarophile in [2 + 3] cycloaddition reactions with allenyl-type three-atom components: DFT computational study.

Jasiński R - Monatsh. Chem. (2015)

Key structures for reaction between nitroacetylene (1) and benzonitrile N-oxide (2a) in toluene according to DFT calculations at B3LYP/6-31G(d) theory level
© Copyright Policy - OpenAccess
Related In: Results  -  Collection

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getmorefigures.php?uid=PMC4495019&req=5

Fig3: Key structures for reaction between nitroacetylene (1) and benzonitrile N-oxide (2a) in toluene according to DFT calculations at B3LYP/6-31G(d) theory level
Mentions: So, in the case of a reaction with benzonitrile N-oxide in toluene, the bond at the β carbon atom introduced from nitroacetylene always is more advanced at the TS (Fig. 3). Formation of bonds in the area of the less favoured energetically TSB takes place in a more asynchronous manner (∆l > 0.2). Both TSs have a polar nature, which is reflected in the value of GEDT index (see Table 2).Fig. 3

Bottom Line: [2 + 3] Cycloaddition reactions of nitroacetylene with allenyl-type three-atom components take place according to the polar, but a one-step mechanism.Alternatively to cycloadducts, during the reaction between the aforementioned reagents, zwitterionic structures with "extended" conformation may be formally created.However, this route is supported by neither kinetic nor thermodynamic factors.

View Article: PubMed Central - PubMed

Affiliation: Institute of Organic Chemistry and Technology, Cracow University of Technology, Cracow, Poland.

ABSTRACT

Abstract: [2 + 3] Cycloaddition reactions of nitroacetylene with allenyl-type three-atom components take place according to the polar, but a one-step mechanism. Alternatively to cycloadducts, during the reaction between the aforementioned reagents, zwitterionic structures with "extended" conformation may be formally created. However, this route is supported by neither kinetic nor thermodynamic factors.

No MeSH data available.