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

被引：26

作者：

Pedersen, Stephan K. ^{[1
]}

Ulfkjaer, Anne ^{[1
]}

Newman, Madeleine N. ^{[1
]}

Yogarasa, Sarangki ^{[1
]}

Petersen, Anne U. ^{[1
]}

Solling, Theis I. ^{[1
]}

Pittelkow, Michael ^{[1
]}

机构：

[1] Univ Copenhagen, Dept Chem, Univ Pk 5, DK-2100 Copenhagen, Denmark

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2018年 / 83卷 / 19期

关键词：

LIGHT PHOTOREDOX CATALYSIS; DERIVATIVES; CONVERSION; PHENOLS;

D O I：

10.1021/acs.joc.8b01800

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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.

引用

页码：12000 / 12006

页数：7

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