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

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

Journal

Journal of Organic Chemistry
ISSN: 1520-6904 , E-ISSN: 0022-3263

Output data

Year: 2018, Volume: 83, Number: 21, Pages: 13427-13445 Pages count : 19 DOI: 10.1021/acs.joc.8b02218

Authors

Vil Vera A. ¹ , Gomes Gabriel dos Passos ² , Ekimova Maria V. ^1,3 , Lyssenko Konstantin A. ⁴ , Syroeshkin Mikhail A. ¹ , Nikishin Gennady I. ¹ , Alabugin Igor V. ² , Terent’ev Alexander O. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp, 119991 Moscow, Russian Federation
2	Department of Chemistry and Biochemistry, Florida State University, Tallahassee 32309, United States
3	D. I. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya Square, Moscow 125047, Russian Federation
4	A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, Moscow 119991 Russian Federation

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.

Vil V.A. , Gomes G.d.P. , Ekimova M.V. , Lyssenko K.A. , Syroeshkin M.A. , Nikishin G.I. , Alabugin I.V. , Terent’ev A.O.
Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF3-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones
Journal of Organic Chemistry. 2018. V.83. N21. P.13427-13445. DOI: 10.1021/acs.joc.8b02218 WOS Scopus OpenAlex

Web of science:	WOS:000449443200045
Scopus:	2-s2.0-85055708275
OpenAlex:	W2897011620

DB	Citing
OpenAlex	25
Scopus	23
Web of science	24