The origin of regio- and stereoselectivity in the 1,3-dipolar cycloaddition of nitrile oxides with C1-substituted 7-oxabenzonorbornadienes, a DFT study

J. Tajabadi; M. Bakavoli; M. Gholizadeh; H. Eshghi; M. Izadyar

doi:10.1039/C5RA04254B

The origin of regio- and stereoselectivity in the 1,3-dipolar cycloaddition of nitrile oxides with C₁-substituted 7-oxabenzonorbornadienes, a DFT study

J. Tajabadi,*^a M. Bakavoli,*^a M. Gholizadeh,^a H. Eshghi^a and M. Izadyar^a

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^a Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad 91775-1436, Iran
E-mail: javad.tajabadi@stu.um.ac.ir, mbakavoli@um.ac.ir
Fax: +98 5138795457
Tel: +98 5138795457

Abstract

In this computational study, density functional theory (DFT) calculations were performed in order to achieve a deep understanding of the regio- and stereoselectivity of 1,3-dipolar cycloadditions (1,3-DC) of C₁-substituted 7-oxabenzonorbornadienes (OBNDs) (2a–2d) with acetonitrile oxide (1a) and benzonitrile oxide (1b). The potential energy surface analysis, Wiberg bond orders (BOs) and global electron density transfer (GEDT) at the transition states (TSs) show that these cycloadditions take place through a low asynchronous one-step mechanism with non-polar character. Mechanism studies show that these reactions are exo-stereoselective and anti-regioselective (3X) and classified as (pseudodiradical) pr-type 1,3-DC reactions. These results are in excellent agreement with the experimental observations. A distortion-interaction model has been used successfully for understanding regio- and stereoselectivity in these reactions.

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The article was received on 10 Mar 2015, accepted on 17 Apr 2015 and first published on 20 Apr 2015

Article type: Paper

DOI: 10.1039/C5RA04254B

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Citation: RSC Adv., 2015,5, 38489-38498

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The origin of regio- and stereoselectivity in the 1,3-dipolar cycloaddition of nitrile oxides with C₁-substituted 7-oxabenzonorbornadienes, a DFT study

J. Tajabadi, M. Bakavoli, M. Gholizadeh, H. Eshghi and M. Izadyar, RSC Adv., 2015, 5, 38489
DOI: 10.1039/C5RA04254B
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The origin of regio- and stereoselectivity in the 1,3-dipolar cycloaddition of nitrile oxides with C₁-substituted 7-oxabenzonorbornadienes, a DFT study

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The origin of regio- and stereoselectivity in the 1,3-dipolar cycloaddition of nitrile oxides with C₁-substituted 7-oxabenzonorbornadienes, a DFT study

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