Laccase/2,2,6,6-Tetramethylpiperidinoxyl Radical (TEMPO): An Efficient Catalytic System for Selective Oxidations of Primary Hydroxy and Amino Groups in Aqueous and Biphasic Media

Copper salts/2,2,6,6‐tetramethylpiperidinoxyl radical (TEMPO) catalytic systems enable efficient aerobic oxidations of primary alcohols but they generally show a reduced reactivity in aqueous medium. Herein, we report an oxidative catalytic system composed of Trametes versicolor laccase and TEMPO, which is able to work in buffer solutions at room temperature using ambient air. Although this catalytic system displays great efficiency in aqueous systems, the addition of methyl tert‐butyl ether allows the reduction of TEMPO loading, also enhancing the solubility of hydrophobic compounds. This practical methodology promotes the chemoselective aerobic oxidation of hydroxy or amino groups, leading to interesting organic derivatives such as aldehydes, lactones, hemiaminals or lactams.