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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.


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Mentions: In particular, very little is known about the simple representative of this group of compounds—parent nitroacetylene (1). Recently, the preliminary results of experimental studies related to nitroacetylene as a Diels–Alder reaction component were published [2]. However, no systematic studies of its participation in reactions of [2 + 3] cycloaddition have been performed to date. This work initiates research in this area; in particular, within the study, complex, quantum-chemical studies of the [2 + 3] cycloaddition reaction of nitroacetylene (1) to selected allenyl-type three-atom components (TACs). Three such TACs were selected, often tested in recent years as components of [2 + 3] cycloaddition reactions with electrophilic ethylenes: benzonitrile N-oxide (2a) [3–6], phenyl azide (2b) [6–8], and phenyldiazomethane (2c) [6, 9] (Scheme 1).


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

Jasiński R - Monatsh. Chem. (2015)

© Copyright Policy - OpenAccess
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC4495019&req=5

Mentions: In particular, very little is known about the simple representative of this group of compounds—parent nitroacetylene (1). Recently, the preliminary results of experimental studies related to nitroacetylene as a Diels–Alder reaction component were published [2]. However, no systematic studies of its participation in reactions of [2 + 3] cycloaddition have been performed to date. This work initiates research in this area; in particular, within the study, complex, quantum-chemical studies of the [2 + 3] cycloaddition reaction of nitroacetylene (1) to selected allenyl-type three-atom components (TACs). Three such TACs were selected, often tested in recent years as components of [2 + 3] cycloaddition reactions with electrophilic ethylenes: benzonitrile N-oxide (2a) [3–6], phenyl azide (2b) [6–8], and phenyldiazomethane (2c) [6, 9] (Scheme 1).

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.