α-Sulfonylated ketazine synthesis from vinyl azides and sodium sulfinates using CAN: radical C–S/N–N coupling cascade as a key reaction pathway

α-Sulfonylated ketazine synthesis from vinyl azides and sodium sulfinates using CAN: radical C–S/N–N coupling cascade as a key reaction pathway Full article

Journal

Organic Chemistry Frontiers
ISSN: 2052-4110 , E-ISSN: 2052-4129

Output data

Year: 2025, Volume: 12, Number: 19, Pages: 5271-5278 Pages count : 8 DOI: 10.1039/d5qo00508f

Authors

Doronin Mikhail M. ¹ , Klikushin Alexander S. ^2,1 , Mulina Olga M. ¹ , Medvedev Michael G. ¹ , Vil’ Vera A. ¹ , He Liang-Nian ³ , Terent'ev Alexander O. ^2,1

Affiliations

1	Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospect, Moscow, 119991, Russian Federation
2	Mendeleev University of Chemical Technology of Russia, 9 Miusskaya Square, Moscow 125047, Russian Federation
3	State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China

Synthesis of α-sulfonylated ketazines from vinyl azides and sodium sulfinates proceeding via radical C–S/N–N coupling cascade has been developed. The cascade starts from the generation of sulfonyl radicals through RSO2Na oxidation by cerium(IV) ammonium nitrate (CAN). Their addition to the double bond of vinyl azides, followed by N2 elimination, leads to the formation of iminyl radicals, whose N–N coupling provides α-sulfonylated ketazines in yields up to 96%. This process represents one of the rare facets of iminyl radical reactivity, namely, N–N radical coupling while bypassing their reduction, intramolecular cyclization, and 1,n-HAT that are typical for them. The EPR-spectra study and quantum chemical calculations revealed that the selective N–N coupling of iminyl radicals was facilitated by the inertness of Ce(III) towards coordination with iminyl radicals and the inaccessibility of charge transfer. In contrast, Mn(II) coordinates with iminyl radicals and converts them into enamines.

Doronin M.M. , Klikushin A.S. , Mulina O.M. , Medvedev M.G. , Vil’ V.A. , He L-N. , Terent'ev A.O.
α-Sulfonylated ketazine synthesis from vinyl azides and sodium sulfinates using CAN: radical C–S/N–N coupling cascade as a key reaction pathway
Organic Chemistry Frontiers. 2025. V.12. N19. P.5271-5278. DOI: 10.1039/d5qo00508f WOS Scopus OpenAlex

Web of science:	WOS:001493149700001
Scopus:	2-s2.0-105005855386
OpenAlex:	W4410500754

DB	Citing
OpenAlex	Нет цитирований
Scopus	Нет цитирований