Exploring α-electron-deficiency-induced [1,2]-fluorine migration†
Abstract
The present study investigates the standard model of [1,2]-fluorine migration and that triggered by the rearrangement of cyclopropyl-substituted fluoroepoxides. The [1,2]-fluorine migration reaction proceeds via a synchronous concerted, tight-ion-pair mechanism. When coupled with other reaction coordinates, the whole reaction follows an asynchronous mechanism, while the [1,2]-fluorince migration unit still retains its tight-ion-pair feature and the reaction coordinates of two C–F distances vary synchronously. A general reaction program for α-electron-deficiency-induced [1,2]-fluorine migration is proposed through an analysis of the intermediates generated from nucleophilic addition. The reaction mechanisms associated with α-electron deficiency and the rearrangement are scrutinized using computational chemistry. Two additional reaction programs for [1,2]-fluorine migration are identified. The Gibbs free energy change of [1,2]-fluorine migration exhibits a linear dependence on the value of the Fukui function of the substrate, which could lead to the production of the desired α-monofluoroketone and enhance the utilization of fluorine atoms.
![Graphical abstract: Exploring α-electron-deficiency-induced [1,2]-fluorine migration](/en/Image/Get?imageInfo.ImageType=GA&imageInfo.ImageIdentifier.ManuscriptID=D3OB01335A&imageInfo.ImageIdentifier.Year=2023)
- This article is part of the themed collection: Computational Organic Chemistry
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