Copper-Mediated Direct Alkoxylation of Arenes Using an <i>N</i>,<i>O</i>‑Bidentate Directing System

Highly effective CuCl-mediated CH alkoxylation of arenes and heteroarenes has been developed by using a 2-aminopyridine 1-oxide moiety as an <i>N</i>,<i>O</i>-bidentate directing group. The reaction proceeds smoothly using a broad range of substrates to afford <i>o</i>-alkoxylated benzoic and heteroaromatic amide products. Moreover, the reaction system shows remarkable compatibility when hexafluoroisopropanol is used as a coupling parter; halogen, nitro, ether, alkoxy, ester, and sulfonyl functional groups are all tolerated. The directing group can be easily removed by base hydrolysis, affording <i>o</i>-alkoxylated benzoic acids