Ozone-Free Synthesis of Ozonides: Assembling Bicyclic Structures from 1,5-Diketones and Hydrogen Peroxide

Ozone-Free Synthesis of Ozonides: Assembling Bicyclic Structures from 1,5-Diketones and Hydrogen Peroxide Full article

Journal

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

Output data

Year: 2018, Volume: 83, Number: 8, Pages: 4402-4426 Pages count : 25 DOI: 10.1021/acs.joc.8b00130

Authors

Yaremenko Ivan A. ^1,2,3 , Gomes Gabriel dos Passos ⁴ , Radulov Peter S. ^1,3 , Belyakova Yulia Yu. ^2,3 , Vilikotskiy Anatoliy E. ^2,3 , Vil Vera A. ^1,2,3 , Korlyukov Alexander A. ^5,6 , Nikishin Gennady I. ³ , Alabugin Igor V. ⁴ , Terent’ev Alexander O. ^1,2,3

Affiliations

1	All-Russian Research Institute for Phytopathology, B. Vyazyomy, Moscow 143050, Russian Federation
2	D. I. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya Square, Moscow 125047, Russian Federation
3	Russian Academy of Sciences, N. D. Zelinsky Institute of Organic Chemistry Russian, 47 Leninsky Prospect, Moscow 119991, Russian Federation
4	Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32313, United States
5	Pirogov Russian National Research Medical University, 1 Ostrovitianov Street, Moscow 117997, Russian Federation
6	Russian Academy of Sciences, A. N. Nesmeyanov Institute of Organoelement Compounds, 28 Vavilov Street, Moscow 119991, Russian Federation

Reactions of 1,5-diketones with H2O2 open an ozone-free approach to ozonides. Bridged ozonides are formed readily at room temperature in the presence of strong Brønsted or Lewis acids such as H2SO4, p-TsOH, HBF4, or BF3·Et2O. The expected bridged tetraoxanes, the products of double H2O2 addition, were not detected. This procedure is readily scalable to produce gram quantities of the ozonides. Bridged ozonides are stable and can be useful as building blocks for bioconjugation and further synthetic transformations. Although less stabilized by anomeric interactions than bis-peroxides, ozonides have an intrinsic advantage of having only one weak O–O bond. The role of the synergetic framework of anomeric effects in bis-peroxides is to overcome this intrinsic disadvantage. As the computational data have shown, this is only possible when all anomeric effects in bis-peroxides are activated to their fullest degree. Consequently, the cyclization selectivity is determined by the length of the bridge between the two carbonyl groups of the diketone. The generally large thermodynamic preference for the formation of cyclic bis-peroxides disappears when 1,5-diketones are used as the bis-cyclization precursors. Stereoelectronic analysis suggests that the reason for the bis-peroxide absence is the selective deactivation of anomeric effects in a [3.2.2]tetraoxanonane skeleton by a structural distortion imposed on the tetraoxacyclohexane subunit by the three-carbon bridge.

Yaremenko I.A. , Gomes G.d.P. , Radulov P.S. , Belyakova Y.Y. , Vilikotskiy A.E. , Vil V.A. , Korlyukov A.A. , Nikishin G.I. , Alabugin I.V. , Terent’ev A.O.
Ozone-Free Synthesis of Ozonides: Assembling Bicyclic Structures from 1,5-Diketones and Hydrogen Peroxide
Journal of Organic Chemistry. 2018. V.83. N8. P.4402-4426. DOI: 10.1021/acs.joc.8b00130 WOS Scopus OpenAlex

≡ Web of science:	WOS:000430898500011
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