A B3LYP/6-31G(d) study of Diels-Alder reactions between cyclopentadiene and (E)-2-arylnitroethenes

• Authors: Radomir Jasiński , Oskar Koifman , Andrzej Barański
• Languages of publication: EN

Abstracts

EN

The B3LYP/6-31G(d) simulations of competing CDA and HDA reactions between cyclopentadiene and (E)-2-arylnitroethenes prove that regardless of the medium polarity, the processes leading to respective 5-nitro-6-aryl-bicyclo-[2,2,0]-hept-2-enes 3,4 (paths A and B) should be most favoured, and the more electrophilic (E)-2-(p-nitrophenyl)-nitroethene should be more reactive than the less electrophilic (E)-2-(p-methoxyphenyl)-nitroethene. Asymmetry of the transition complexes on the favoured pathways increases with increase of medium polarity, but not sufficiently to enforce the zwitterionic mechanism. Analysis of competing pathways leading to HDA adducts proves that not all these compounds can be formed directly from the adducts. In particular, on the path C, the initially formed 5-nitro-6-aryl-bicyclo-[2,2,0]-hept-2-enes 3 is converted to 2-phenyl-4-aza-5-oxy-bicyclo-[3,4,0]-nona-3,7-diene N-oxides 5 as a result of a [3.3]-sigmatropic shift. On the paths D–F leading to 2-phenyl-4-aza-5-oxy-bicyclo-[3,4,0]-nonadienes N-oxides 6–8, the reaction proceeds according to a one-step mechanism. [...]

Keywords

EN

Diels-Alder reaction; Nitroalkene; Cyclopentadiene; B3LYP/6-31G(d); Mechanism

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2011
• Volume: 9
• Issue: 6
• Pages: 1008-1018

Dates

published

1 - 12 - 2011

online

27 - 9 - 2011

Contributors

author

Radomir Jasiński

• Institute of Organic Chemistry and Technology, Cracow University of Technology, 31155, Cracow, Poland

author

Oskar Koifman

• Faculty of Organic Chemistry and Technology, Ivanovo State University of Chemistry and Technology, 153000, Ivanovo, Russian Federation

author

Andrzej Barański

• Institute of Organic Chemistry and Technology, Cracow University of Technology, 31155, Cracow, Poland

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Identifiers

DOI

10.2478/s11532-011-0088-5