Organic and Biomolecular Chemistry, Year (2016-7)

Title : ( A mechanistic insight into the effect of piperidine as an organocatalyst on the [3 + 2] cycloaddition reaction of benzalacetone with phenyl azide from a computational study )

Authors: javad tajabadi , Mehdi Bakavoli , Mostafa Gholizadeh , Hossein Eshghi ,

Access to full-text not allowed by authors

Citation: BibTeX | EndNote

Several transition structures (TSs) for catalyst-free [3 + 2] cycloaddition and two plausible mechanistic pathways for the organocatalyzed [3 + 2] cycloaddition (32CA) between benzalacetone and phenyl azide were located by quantum chemistry methods. Calculations were carried out with B3LYP, MPWB1K and M06-2X functionals using 6-31G(d) and 6-311G(d,p) basis sets in gas and solvent phases. The calculated activation barriers imply that the lowest barrier pathway is the catalyzed process producing 3-regioisomers through the iminium intermediate and not through the dienamine route. Electronic displacements along the reaction path have been examined using a topological analysis of the electronlocalization function (ELF). ELF topological analyses along the intrinsic reaction coordinates (IRC) of both catalyzed and uncatalyzed 32CA reactions indicated that while the first C1–N1 single bond is formed as a dative bond, the formation of the second C2–N3 bond takes place via a C-to-N coupling between the interacting centers of the reagents. Moreover, the ELF analyses imply that the reaction mechanism is a two-stage one-step process in the presence of a piperidine organocatalyst, while bond formation in an uncatalyzed process is almost synchronous

Keywords

, catalyst-free, [3 + 2] cycloaddition, mechanistic pathways, organocatalyzed [3 + 2] cycloaddition
برای دانلود از شناسه و رمز عبور پرتال پویا استفاده کنید.

@article{paperid:1057319,
author = {Tajabadi, Javad and Bakavoli, Mehdi and Gholizadeh, Mostafa and Eshghi, Hossein},
title = {A mechanistic insight into the effect of piperidine as an organocatalyst on the [3 + 2] cycloaddition reaction of benzalacetone with phenyl azide from a computational study},
journal = {Organic and Biomolecular Chemistry},
year = {2016},
month = {July},
issn = {1477-0520},
keywords = {catalyst-free; [3 + 2] cycloaddition; mechanistic pathways; organocatalyzed [3 + 2] cycloaddition (32CA);},
}

[Download]

%0 Journal Article
%T A mechanistic insight into the effect of piperidine as an organocatalyst on the [3 + 2] cycloaddition reaction of benzalacetone with phenyl azide from a computational study
%A Tajabadi, Javad
%A Bakavoli, Mehdi
%A Gholizadeh, Mostafa
%A Eshghi, Hossein
%J Organic and Biomolecular Chemistry
%@ 1477-0520
%D 2016

[Download]