Issue 28, 2015

Regio- and diastereoselectivity of the 1,3-dipolar cycloaddition of α-aryl nitrone with methacrolein. A theoretical investigation

Abstract

The mechanism, regio- and diastereoselectivity of the 1,3-dipolar cycloaddition of N-iso-propyl,α-(4-trifluoromethyl)-phenyl nitrone with methacrolein yielding the isoxazolidine cycloadduct [V. Bãdoiu, E. P. Kündig, Org. Biomol. Chem., 2012, 10, 114] has been studied at the B3LYP/6-31G(d) level of theory. The two conformations s-cis and s-trans of methacrolein are considered in the cyclisation modes and all the possible regio-(ortho/meta) and stereo-(endo/exo) isomeric channels to provide the different diastereoisomers were thoroughly investigated. The free activation enthalpies, calculated with the MPW1B95/6-31G(d) method, in dichloromethane show that the meta-endo channel corresponding to the cyclisation mode between the nitrone and the s-cis methacrolein giving the RR/SS diastereoisomers is the most favoured reaction channel as expected experimentally. Intrinsic reaction coordinate (IRC) calculations and the topological analysis of the electron localization function (ELF) of some relevant points of the IRC curve show that the meta-endo favoured channel takes place via a one-step non-concerted mechanism. Charge transfer calculations performed in the transition states in combination with the calculation of DFT-based reactivity indices of the reactants reveal a low polar character of the studied reaction.

Graphical abstract: Regio- and diastereoselectivity of the 1,3-dipolar cycloaddition of α-aryl nitrone with methacrolein. A theoretical investigation

Supplementary files

Article information

Article type
Paper
Submitted
30 Dec 2014
Accepted
16 Feb 2015
First published
18 Feb 2015

RSC Adv., 2015,5, 22126-22134

Author version available

Regio- and diastereoselectivity of the 1,3-dipolar cycloaddition of α-aryl nitrone with methacrolein. A theoretical investigation

W. Benchouk and S. M. Mekelleche, RSC Adv., 2015, 5, 22126 DOI: 10.1039/C4RA17285J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements