Inverse α-Effect as the Ariadne’s Thread on the Way to Tricyclic Aminoperoxides: Avoiding Thermodynamic Traps in the Labyrinth of Possibilities

Inverse α-Effect as the Ariadne’s Thread on the Way to Tricyclic Aminoperoxides: Avoiding Thermodynamic Traps in the Labyrinth of Possibilities Full article

Journal

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

Output data

Year: 2022, Volume: 144, Number: 16, Pages: 7264-7282 Pages count : 19 DOI: 10.1021/jacs.2c00406

Authors

Yaremenko Ivan A. ¹ , Belyakova Yulia Yu. ¹ , Radulov Peter S. ¹ , Novikov Roman A. ¹ , Medvedev Michael G. ¹ , Krivoshchapov Nikolai V. ^2,1 , Korlyukov Alexander A. ³ , Alabugin Igor V. ⁴ , Terent'ev Alexander O. ¹

Affiliations

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

Stable tricyclic aminoperoxides can be selectively assembled via a catalyst-free three-component condensation of β,δ′-triketones, H2O2, and an NH-group source such as aqueous ammonia or ammonium salts. This procedure is scalable and can produce gram quantities of tricyclic heterocycles, containing peroxide, nitrogen, and oxygen cycles in one molecule. Amazingly, such complex tricyclic molecules are selectively formed despite the multitude of alternative reaction routes, via equilibration of peroxide, hemiaminal, monoperoxyacetal, and peroxyhemiaminal functionalities! The reaction is initiated by the “stereoelectronic frustration” of H2O2 and combines elements of thermodynamic and kinetic control with a variety of mono-, bi-, and tricyclic structures evolving under the conditions of thermodynamic control until they reach a kinetic wall created by the inverse α-effect, that is, the stereoelectronic penalty for the formation of peroxycarbenium ions and related transition states. Under these conditions, the reaction stops before reaching the most thermodynamically stable products at a stage where three different heterocycles are assembled and fused at the acyclic precursor frame.

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.
Inverse α-Effect as the Ariadne’s Thread on the Way to Tricyclic Aminoperoxides: Avoiding Thermodynamic Traps in the Labyrinth of Possibilities
Journal of the American Chemical Society. 2022. V.144. N16. P.7264-7282. DOI: 10.1021/jacs.2c00406 WOS Scopus OpenAlex

Web of science:	WOS:000799141600029
Scopus:	2-s2.0-85128691572
OpenAlex:	W4223970269

DB	Citing
OpenAlex	22
Scopus	19
Web of science	15