Inverting the Selectivity of the Newman-Kwart Rearrangement via One Electron Oxidation at Room Temperature

The Journal of Organic Chemistry
Stephan K PedersenMichael Pittelkow

Abstract

The discovery that the Newman-Kwart rearrangement can be performed at room temperature by action of a simple and readily available oxidant, cerium ammonium nitrate, is described. The conditions give clean conversion when using electron-rich aromatic substrates, and the reactions are often quantitative. Computational studies support a reaction mechanism where the O-thiocarbamate is first oxidized to the radical cation, followed by nucleophilic attack by the ipso carbon of the aromatic system.

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Citations

Apr 17, 2019·Angewandte Chemie·Simon RohrbachJohn A Murphy
Aug 28, 2020·Chemical Communications : Chem Comm·Connor A LawsonJohn A Murphy
Feb 23, 2021·Chemical Communications : Chem Comm·Debarshi SahaPrabal Banerjee
Sep 4, 2019·The Journal of Organic Chemistry·Annie K GilbertMichael D Pluth
Nov 30, 2018·Organic Letters·Timo BroeseRobert Francke
Jan 24, 2019·The Journal of Organic Chemistry·Sina Chiniforoush, Christopher J Cramer
Dec 19, 2019·Organic Letters·Thibault GendronErik Årstad
Mar 25, 2020·Organic Letters·Sourav Sekhar Bera, Modhu Sudan Maji

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