Molecular-Oxygen-Mediated\nMulticomponent Oxidative\nCyclization: Synthesis of Tertiary-Alcohol-Unit-Bearing <i>N</i>‑Heterocycles via Transforming C–H to C–OH Bonds

We developed a molecular-oxygen-mediated multicomponent\noxidative\ncyclization strategy to synthesize <i>N</i>-heterocycles\ncontaining tertiary alcohol units via the formation of key C–OH\nbonds and quaternary carbon centers. This formal [3 + 2 + 1] annulation\noffers a green and sustainable alternative for the <i>de novo</i> C–OH bond formation, using O<sub>2</sub> as both the oxidant\nand oxygen source under metal- and catalyst-free conditions. Notably,\ncontinuous [1,5]-hydrogen transfer together with excess alcohols promotes\nthe formation of C–OH-bearing products. Additionally, the generation\nof quaternary carbon centers inhibits the conversion of C–OH\nbonds to CO bonds, thus stabilizing the desired products.