Free Radicals in the Queue: Selective Successive Addition of Azide and N-Oxyl Radicals to Alkenes

Free Radicals in the Queue: Selective Successive Addition of Azide and N-Oxyl Radicals to Alkenes Full article

Journal

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

Output data

Year: 2023, Volume: 88, Number: 18, Pages: 13225-13235 Pages count : 11 DOI: 10.1021/acs.joc.3c01470

Authors

Lopat’eva Elena R. ¹ , Krylov Igor B. ^2,1 , Paveliev Stanislav A. ¹ , Emtsov Daniil A. ^2,1 , Kostyagina Vera A. ^2,1 , Korlyukov Alexander A. ³ , Terent’ev Alexander O. ^2,1

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospekt, 119991 Moscow, Russia
2	D. I. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya Square, 125047 Moscow, Russia
3	Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov strasse, 28, 119991 Moscow, Russia

The selective successive addition of azide (•N3) and N-oxyl radicals to alkenes is demonstrated, despite each of the two radicals being known to attack C═C bonds and the mixture of radical adducts possibly being expected. The proposed radical mechanism was supported by density functional theory calculations, electron paramagnetic resonance, and radical trapping experiments. The reaction proceeds at room temperature with the available reagents: NaN3, N-hydroxy compounds, and PhI(OAc)2 as the oxidant. The method can be applied for N-hydroxyimides, N-hydroxyamides, N-hydroxybenzotriazole, and oximes as N-oxyl radical precursors. Vinylarenes, aliphatic alkenes, and even electron-deficient methyl methacrylate were successfully functionalized.

Lopat’eva E.R. , Krylov I.B. , Paveliev S.A. , Emtsov D.A. , Kostyagina V.A. , Korlyukov A.A. , Terent’ev A.O.
Free Radicals in the Queue: Selective Successive Addition of Azide and N-Oxyl Radicals to Alkenes
Journal of Organic Chemistry. 2023. V.88. N18. P.13225-13235. DOI: 10.1021/acs.joc.3c01470 WOS Scopus OpenAlex

Web of science:	WOS:001068548200001
Scopus:	2-s2.0-85169918706
OpenAlex:	W4386148270

DB	Citing
OpenAlex	8
Scopus	6
Web of science	9