Title : ( Density functional theory study of the regio- and stereoselectivity of 1,3-dipolar cycloaddition reactions between 2-ethylthio-4- phenyl-1-azetin and some substituted nitrile oxides )
Authors: Amir khojastehnezhad golmakani , Hossein Eshghi , Farid Moeinpour , Mehdi Bakavoli , Mohammad Izadyar , javad tajabadi ,
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Abstract
The mechanism (regio- and stereoselectivity) of 1,3-dipolar cycloaddition (1,3-DC) of 2-ethylthio-4-phenyl-1-azetin 1 with benzonitrile oxide 2a, 2-aminobenzonitrile oxide 2b and 2-azidobenzonitrile oxide 2c has been investigated by density functional theory-based reactivity indices and activation energy calculations at B3LYP/6-31G(d,p) level of theory in the gas and solvent phase. Thermodynamic and kinetic parameters of the possible ortho/meta regioisomeric and endo/exo stereoisomeric pathways have been determined. In order to rationalize complete endo selective fashion provided by these 1,3-DC cycloadditions, a natural steric analysis between NLMOs i,j for TS1ox and TS1on and also a second-order interaction energy, E2, analysis between the donor–acceptor orbitals in these TSs were carried out. In all cases, the ortho pathways are more favorable compared to the meta alternatives and it is found that the endo pathway is preferred. Our results show that these cycloadditions follow an asynchronous one-step mechanism with a nonpolar character. Theoretical data are in good agreement with the experimental results.
Keywords
, Regioselectivity, Stereoselectivity, 1, 3-Dipolar cycloaddition, 2-ethylthio-4-phenyl-1-azetin, DFT reactivity indices
@article{paperid:1055639,
author = {Khojastehnezhad Golmakani, Amir and Eshghi, Hossein and Farid Moeinpour and Bakavoli, Mehdi and Izadyar, Mohammad and Tajabadi, Javad},
title = {Density functional theory study of the regio- and stereoselectivity of 1,3-dipolar cycloaddition reactions between 2-ethylthio-4- phenyl-1-azetin and some substituted nitrile oxides},
journal = {Structural Chemistry},
year = {2016},
volume = {27},
number = {4},
month = {August},
issn = {1040-0400},
pages = {1041--1047},
numpages = {6},
keywords = {Regioselectivity; Stereoselectivity; 1;3-Dipolar cycloaddition; 2-ethylthio-4-phenyl-1-azetin;DFT reactivity indices},
}
%0 Journal Article
%T Density functional theory study of the regio- and stereoselectivity of 1,3-dipolar cycloaddition reactions between 2-ethylthio-4- phenyl-1-azetin and some substituted nitrile oxides
%A Khojastehnezhad Golmakani, Amir
%A Eshghi, Hossein
%A Farid Moeinpour
%A Bakavoli, Mehdi
%A Izadyar, Mohammad
%A Tajabadi, Javad
%J Structural Chemistry
%@ 1040-0400
%D 2016
