A DFT study of the mechanism and the regioselectivity of [3 + 2] cycloaddition reactions of nitrile oxides with α, β-acetylenic aldehyde. (1st November 2016)

• Record Type: Journal Article
• Authors: Sobhi, Chafia; Nacereddine, Abdelmalek Khorief; Nasri, Lilia; Lechtar, Zohra; Djerourou, Abdelhafid
• Is Part Of: Molecular physics. Volume 114:Number 21(2016)
• Page Start: 3193
• Page End: 3200
• Publication Date: 2016-11-01
• Subjects: [3 + 2] Cycloaddition reaction -- nitrile oxide -- alkyne -- DFT calculations -- reactivity indices -- regioselectivity; Molecules -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Molécules -- Périodiques; Chimie physique et théorique -- Périodiques; 539.6.05
• DOI: 10.1080/00268976.2016.1224395
• Languages: English
• ISSNs: 0026-8976

Abstract

ABSTRACT: A DFT study of the (32CA) reaction of a series of some nitrile oxides with electron-deficient alkyne (3-phenylpropionlaldehyde) in gas phase and in toluene has been carried out using B3LYP functional with 6-31G(d) basis set. Two reactive channels 4- and 5-associated with the two regioisomeric modes have been located and characterised. These 32CA reactions are characterised by a low asynchronous one-step mechanism with a low-polar character. Analysis of the DFT reactivity indices indicates that the nucleophilic centre of the different nitrile oxides accounts for the 4-regioselectivity. Our calculations are in a good agreement with the experimental findings. Abstract :