Marriage of Peroxides and Nitrogen Heterocycles: Selective Three-Component Assembly, Peroxide-Preserving Rearrangement, and Stereoelectronic Source of Unusual Stability of Bridged Azaozonides

Marriage of Peroxides and Nitrogen Heterocycles: Selective Three-Component Assembly, Peroxide-Preserving Rearrangement, and Stereoelectronic Source of Unusual Stability of Bridged Azaozonides Full article

Journal

Journal of the American Chemical Society
ISSN: 0002-7863 , E-ISSN: 1520-5126

Output data

Year: 2021, Volume: 143, Number: 17, Pages: 6634-6648 Pages count : 15 DOI: 10.1021/jacs.1c02249

Authors

Yaremenko Ivan A. ¹ , Belyakova Yulia Yu. ¹ , Radulov Peter S. ¹ , Novikov Roman A. ¹ , Medvedev Michael G. ¹ , Krivoshchapov Nikolai V. ¹ , Korlyukov Alexander A. ² , Alabugin Igor V. ³ , Terent’ev Alexander O. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospekt, 119991 Moscow, Russian Federation
2	A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova Street, 119991 Moscow, Russian Federation
3	Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States

Stable bridged azaozonides can be selectively assembled via a catalyst-free three-component condensation of 1,5-diketones, hydrogen peroxide, and an NH-group source such as aqueous ammonia or ammonium salts. This procedure is scalable and can produce gram quantities of bicyclic stereochemically rich heterocycles. The new azaozonides are thermally stable and can be stored at room temperature for several months without decomposition and for at least 1 year at −10 °C. The chemical stability of azaozonides was explored for their subsequent selective transformations including the first example of an aminoperoxide rearrangement that preserves the peroxide group. The amino group in aminoperoxides has remarkably low nucleophilicity and does not participate in the usual amine alkylation and acylation reactions. These observations and the 15 pKa units decrease in basicity in comparison with a typical dialkyl amine are attributed to the strong hyperconjugative nN→σ*C–O interaction with the two antiperiplanar C–O bonds. Due to the weakness of the complementary nO→σ*C–N donation from the peroxide oxygens (a consequence of “inverse α-effect”), this interaction depletes electron density from the NH moiety, protects it from oxidation, and makes it similar in properties to an amide.

Yaremenko I.A. , Belyakova Y.Y. , Radulov P.S. , Novikov R.A. , Medvedev M.G. , Krivoshchapov N.V. , Korlyukov A.A. , Alabugin I.V. , Terent’ev A.O.
Marriage of Peroxides and Nitrogen Heterocycles: Selective Three-Component Assembly, Peroxide-Preserving Rearrangement, and Stereoelectronic Source of Unusual Stability of Bridged Azaozonides
Journal of the American Chemical Society. 2021. V.143. N17. P.6634-6648. DOI: 10.1021/jacs.1c02249 WOS Scopus OpenAlex

Web of science:	WOS:000648704100040
Scopus:	2-s2.0-85105904186
OpenAlex:	W3154461191

DB	Citing
OpenAlex	24
Scopus	23
Web of science	20