Remote Stereoelectronic Effects in Pyrrolidone- and Caprolactam-Substituted Phenols: Discrepancies in Antioxidant Properties Evaluated by Electrochemical Oxidation and H-Atom Transfer Reactivity

Remote Stereoelectronic Effects in Pyrrolidone- and Caprolactam-Substituted Phenols: Discrepancies in Antioxidant Properties Evaluated by Electrochemical Oxidation and H-Atom Transfer Reactivity Научная публикация

Журнал

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

Вых. Данные

Год: 2022, Том: 87, Номер: 8, Страницы: 5371-5384 Страниц : 14 DOI: 10.1021/acs.joc.2c00207

Авторы

Akyeva Anna Ya ¹ , Kansuzyan Artem V ¹ , Vukich Katarina S ^2,1 , Kuhn Leah ³ , Saverina Evgeniya A ¹ , Minyaev Mikhail E ¹ , Pechennikov Valery M ² , Egorov Mikhail P ¹ , Alabugin Igor V ³ , Vorobyev Stepan V ⁴ , Syroeshkin Mikhail A ¹

Организации

1	N.D. Zelinsky Institute of Organic Chemistry, 119991 Moscow Russia
2	I.M. Sechenov First Moscow State Medical University, 119991 Moscow, Russia
3	Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States
4	Gubkin Russian State University of Oil and Gas, 65 Leninsky Prospect, 119991 Moscow, Russia

New antioxidants are commonly evaluated via two main approaches, i.e., the ability to donate an electron and the ability to intercept free radicals. We compared these approaches by evaluating the properties of 11 compounds containing both antioxidant moieties (mono- and polyphenols) and auxiliary pharmacophores (pyrrolidone and caprolactam). Several common antioxidants, such as butylated hydroxytoluene (BHT), 2,3,5-trimethylphenol (TMP), quercetin, and dihydroquercetin, were added for comparison. The antioxidant properties of these compounds were determined by their rates of reaction with 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical and their oxidation potentials from cyclic voltammetry. Although these methods test different chemical properties, their results correlate reasonably well. However, several exceptions exist where the two methods give opposite predictions! One of them is the different behavior of mono- and polyphenols: polyphenols can react with DPPH more than an order of magnitude faster than monophenols of a similar oxidation potential. The second exception stems from the size of a “bystander” lactam ring at the benzylic position. Although the phenols with a seven-membered lactam ring are harder to oxidize, the sterically nonhindered compounds react with DPPH about 2× faster than the analogous five-membered lactams. The limitations of computational methods, especially those based on a single parameter, are also evaluated and discussed.

Akyeva A.Y. , Kansuzyan A.V. , Vukich K.S. , Kuhn L. , Saverina E.A. , Minyaev M.E. , Pechennikov V.M. , Egorov M.P. , Alabugin I.V. , Vorobyev S.V. , Syroeshkin M.A.
Remote Stereoelectronic Effects in Pyrrolidone- and Caprolactam-Substituted Phenols: Discrepancies in Antioxidant Properties Evaluated by Electrochemical Oxidation and H-Atom Transfer Reactivity
Journal of Organic Chemistry. 2022. V.87. N8. P.5371-5384. DOI: 10.1021/acs.joc.2c00207 WOS Scopus OpenAlex

Web of science:	WOS:000792258800029
Scopus:	2-s2.0-85128221451
OpenAlex:	W4224067426

БД	Цитирований
OpenAlex	8
Scopus	7
Web of science	6