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

Stephan K. Pedersen; Anne Ulfkjær; Madeleine N. Newman; Sarangki Yogarasa; Anne U. Petersen; Theis I. Sølling; Michael Pittelkow

doi:10.1021/acs.joc.8b01800

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

Stephan K. Pedersen, Anne Ulfkjær, Madeleine N. Newman, Sarangki Yogarasa, Anne U. Petersen, Theis I. Sølling, Michael Pittelkow

13 Citations (Scopus)

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.

Original language	English
Journal	The Journal of Organic Chemistry
Volume	83
Issue number	19
Pages (from-to)	12000-12006
Number of pages	7
ISSN	0022-3263
DOIs	https://doi.org/10.1021/acs.joc.8b01800
Publication status	Published - 5 Oct 2018

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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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AU - Pedersen, Stephan K.

AU - Ulfkjær, Anne

AU - Newman, Madeleine N.

AU - Yogarasa, Sarangki

AU - Petersen, Anne U.

AU - Sølling, Theis I.

AU - Pittelkow, Michael

PY - 2018/10/5

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N2 - 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.

AB - 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.

U2 - 10.1021/acs.joc.8b01800

DO - 10.1021/acs.joc.8b01800

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SP - 12000

EP - 12006

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

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ER -

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

Abstract

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