Iodine-Catalyzed Radical C–H Amination of Nonaromatic Imidazole Oxides: Access to Cyclic α-Aminonitrones

Iodine-Catalyzed Radical C–H Amination of Nonaromatic Imidazole Oxides: Access to Cyclic α-Aminonitrones Научная публикация

Журнал

Journal of Organic Chemistry
ISSN: 0022-3263

Вых. Данные

Год: 2024, Том: 89, Номер: 1, Страницы: 463-473 Страниц : 11 DOI: 10.1021/acs.joc.3c02230

Авторы

Akulov Alexey A. ¹ , Varaksin Mikhail V. ^1,2 , Nelyubina Anna A. ¹ , Tsmokaluk Anton N. ¹ , Mazhukin Dmitrii G. ³ , Tikhonov Alexsei Y. ³ , Charushin Valery N. ^1,2 , Chupakhin Oleg N. ^1,2

Организации

1	Ural Federal University, 19 Mira Street, Ekaterinburg 620002, Russian Federation
2	I.Ya. Postovsky Institute of Organic Synthesis, 22 S. Kovaleskoy Street, Ekaterinburg 620991, Russian Federation
3	N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, 9 Akademika Lavrentieva Avenue, Novosibirsk 630090, Russian Federation

Abstract A straightforward cross-dehydrogenative coupling approach to incorporate alicyclic amino residues into the structure of model cyclic aldonitrones, 2H-imidazole oxides, is reported. The elaborated C(sp2)–H functionalization is achieved by employing cyclic amines in the presence of the I2–tert-butyl hydroperoxide (TBHP) reagent system. As a result, a series of 19 novel heterocyclic derivatives were obtained in yields of up to 97%. A mechanistic study involving electron paramagnetic resonance spectroscopic experiments allowed the radical nature of the reaction to be confirmed. In particular, the envisioned mechanistic rationale comprises N-iodination of a cyclic amine, followed by N–I bond homolysis of the resulting intermediate and subsequent amination of the nitrone moiety via the newly generated nitrogen-centered radical.

Akulov A.A. , Varaksin M.V. , Nelyubina A.A. , Tsmokaluk A.N. , Mazhukin D.G. , Tikhonov A.Y. , Charushin V.N. , Chupakhin O.N.
Iodine-Catalyzed Radical C–H Amination of Nonaromatic Imidazole Oxides: Access to Cyclic α-Aminonitrones
Journal of Organic Chemistry. 2024. V.89. N1. P.463-473. DOI: 10.1021/acs.joc.3c02230 WOS Scopus

Поступила в редакцию:	30 сент. 2023 г.
Принята к публикации:	4 дек. 2023 г.
Опубликована online:	13 дек. 2023 г.
Опубликована в печати:	5 янв. 2024 г.

Web of science	WOS:001137566300001
Scopus	2-s2.0-85180954306
OpenAlex	W4389702629