American Chemical Society
jo8b02218_si_002.cif (364.72 kB)

Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF3‑Catalyzed Synthesis of β‑Hydroperoxy-β-peroxylactones

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posted on 2018-10-11, 00:00 authored by Vera A. Vil’, Gabriel dos Passos Gomes, Maria V. Ekimova, Konstantin A. Lyssenko, Mikhail A. Syroeshkin, Gennady I. Nikishin, Igor V. Alabugin, Alexander O. Terent’ev
We have discovered synthetic access to β-hydroperoxy-β-peroxylactones via BF3-catalyzed cyclizations of a variety of acyclic precursors, β-ketoesters and their silyl enol ethers, alkyl enol ethers, enol acetates, and cyclic acetals, with H2O2. Strikingly, independent of the choice of starting material, these reactions converge at the same β-hydroperoxy-β-peroxylactone products, i.e., the peroxy analogues of the previously elusive cyclic Criegee intermediate of the Baeyer–Villiger reaction. Computed thermodynamic parameters for the formation of the β-hydroperoxy-β-peroxylactones from silyl enol ethers, enol acetates, and cyclic acetals confirm that the β-peroxylactones indeed correspond to a deep energy minimum that connects a variety of the interconverting oxygen-rich species at this combined potential energy surface. The target β-hydroperoxy-β-peroxylactones were synthesized from β-ketoesters, and their silyl enol ethers, alkyl enol ethers, enol acetates, and cyclic acetals were obtained in 30–96% yields. These reactions proceed under mild conditions and open synthetic access to a broad selection of β-hydroperoxy-β-peroxylactones that are formed selectively even in those cases when alternative oxidation pathways can be expected. These β-peroxylactones are stable and can be useful for further synthetic transformations.