Peroxycarbenium Ions as the “Gatekeepers” in Reaction Design: Assistance from Inverse Alpha‐Effect in Three‐Component β‐Alkoxy‐β‐peroxylactones Synthesis

Peroxycarbenium Ions as the “Gatekeepers” in Reaction Design: Assistance from Inverse Alpha‐Effect in Three‐Component β‐Alkoxy‐β‐peroxylactones Synthesis Full article

Journal

Chemistry: A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765

Output data

Year: 2019, Volume: 25, Number: 63, Pages: 14460-14468 Pages count : 9 DOI: 10.1002/chem.201903752

Authors

Vil' Vera A. ^1,2 , Barsegyan Yana A. ^1,2 , Barsukov Denis V. ¹ , Korlyukov Alexander A. ^3,4 , Alabugin Igor V. ⁵ , Terent'ev Alexander O. ^1,2

Affiliations

1	N. D. Zelinsky Institute of Organic ChemistryRussian Academy of Sciences 47 Leninsky Prospect Moscow 119991 Russian Federation
2	All-Russian Research Institute for Phytopathology B. Vyazyomy Moscow Region 143050 Russian Federation
3	A. N. Nesmeyanov Institute of Organoelement CompoundsRussian Academy of Sciences 28 Vavilov Street Moscow 119991 Russian Federation
4	Pirogov Russian National Research Medical University Moscow 117997 Russian Federation
5	Department of Chemistry and Biochemistry, Florida State University, Tallahassee, 32309 USA

Stereoelectronic interactions control reactivity of peroxycarbenium cations, the key intermediates in (per)oxidation chemistry. Computational analysis suggests that alcohol involvement as a third component in the carbonyl/peroxide reactions remained invisible due to the absence of sufficiently deep kinetic traps needed to prevent the escape of mixed alcohol/peroxide products to the more stable bisperoxides. Synthesis of β-alkoxy-β-peroxylactones, a new type of organic peroxides, was accomplished by interrupting a thermodynamically driven peroxidation cascade. The higher energy β-alkoxy-β-peroxylactones do not transform into the more stable bisperoxides due to the stereoelectronically imposed instability of a cyclic peroxycarbenium intermediate as a consequence of amplified inverse alpha-effect. The practical consequence of this fundamental finding is the first three-component cyclization/condensation of β-ketoesters, H2O2, and alcohols that provides β-alkoxy-β-peroxylactones in 15–80 % yields.

Vil' V.A. , Barsegyan Y.A. , Barsukov D.V. , Korlyukov A.A. , Alabugin I.V. , Terent'ev A.O.
Peroxycarbenium Ions as the “Gatekeepers” in Reaction Design: Assistance from Inverse Alpha‐Effect in Three‐Component β‐Alkoxy‐β‐peroxylactones Synthesis
Chemistry: A European Journal. 2019. V.25. N63. P.14460-14468. DOI: 10.1002/chem.201903752 WOS Scopus OpenAlex

Web of science:	WOS:000490388600001
Scopus:	2-s2.0-85074439755
OpenAlex:	W2971624241

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OpenAlex	18
Scopus	20