TY - JOUR
T1 - Inverting the Selectivity of the Newman–Kwart Rearrangement via One Electron Oxidation at Room Temperature
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
Y1 - 2018/10/5
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
M3 - Journal article
C2 - 30160966
SN - 0022-3263
VL - 83
SP - 12000
EP - 12006
JO - The Journal of Organic Chemistry
JF - The Journal of Organic Chemistry
IS - 19
ER -