Electrochemical Nitrooxylation and NO ₂ Elimination-Grignard Addition for the Oxa-Quaternization of Saturated <i>N</i> -Heterocycles: Access to α-Aryl-α-hydroxy Lactams

The development of an electrochemical nitrooxylation reaction of 3-alkoxyamino lactams <b>A</b> to 3-nitrooxylated lactams <b>B</b> allowed the invention of a NO₂ elimination-Grignard reagent addition for the C3-oxa-quaternization of <i>N</i>-heterocycles. With this novel synthetic technology in hand and taking advantages of the selective dual C-H oxidation of <i>N</i>-heterocyles, various α-aryl-α-hydroxy-lactams <b>C</b> were prepared from simple and saturated pyrrolidines, piperidines, and one azepine, including two bioactive alkaloids.