Computational study on the boundary between the concerted and stepwise mechanism of bimolecular SNAr reactions

Simon Rohrbach; John A. Murphy; Tell Tuttle

doi:10.1021/jacs.0c01975

Computational study on the boundary between the concerted and stepwise mechanism of bimolecular SNAr reactions

Simon Rohrbach, John A. Murphy, Tell Tuttle

Pure And Applied Chemistry

Research output: Contribution to journal › Article

Abstract

The text-book mechanism of bimolecular nucleophilic aromatic substitutions (SNAr) reactions is a stepwise process that proceeds via a so-called Meisenheimer intermediate. Only recently the alternative, concerted version of this mechanism has gained acceptance as more and more examples thereof have been reported. But so far only isolated examples of concerted SNAr reactions have been described and a coherent picture of when a SNAr reaction proceeds via a stepwise and when via a concerted mechanism has not yet been established. Here key factors are identified that influence the mechanistic choice of SNAr reactions. Moreover, the electron affinity is used as a simple descriptor to make a prediction on whether a given aryl fluoride substrate favors a concerted or stepwise mechanism.

Original language	English
Pages (from-to)	14871-14876
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	142
Issue number	35
Early online date	7 Aug 2020
DOIs	https://doi.org/10.1021/jacs.0c01975
Publication status	Published - 20 Aug 2020

Keywords

concerted nucleophilic aromatic substitution
cSNAr
SNAr
DFT
structure-activity relationship

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Accelerated Discovery and Development of New Medicines: Prosperity Partnership for a Healthier Nation

Kerr, W., Brown, C., Florence, A., Jamieson, C., Johnston, B., Murphy, J., Palmer, D. & Tomkinson, N.

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Datasets

Data for: "Computational Study on the Boundary Between the Concerted and Stepwise Mechanism of Bimolecular SNAr Reactions" (2nd Revision)

Tuttle, T. (Creator), Rohrbach, S. (Creator) & Murphy, J. (Contributor), University of Strathclyde, 8 Jun 2020

DOI: 10.15129/254ecae8-9c72-4bb9-9319-b16eada94f9c

Dataset

Cite this

Rohrbach, S., Murphy, J. A., & Tuttle, T. (2020). Computational study on the boundary between the concerted and stepwise mechanism of bimolecular SNAr reactions. Journal of the American Chemical Society, 142(35), 14871-14876. https://doi.org/10.1021/jacs.0c01975

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