An N–O to N/S atom swapping process in 1,2-oxazine N -oxides to access pyrroles and thiophenes

An N–O to N/S atom swapping process in 1,2-oxazine N -oxides to access pyrroles and thiophenes Full article

Journal

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

Output data

Year: 2026, Volume: 13, Number: 18, Pages: 6091-6101 Pages count : 11 DOI: 10.1039/d6qo00597g

Authors

Dvinyaninova Tatiana Y. ^1,2 , Zhirov Alexander V. ^3,2 , Pospelov Evgeny V. ² , Golovanov Ivan S. ² , Sukhorukov Alexey Yu. ²

Affiliations

1	Higher Chemical College, D. Mendeleev University of Chemical Technology of Russia, Miusskaya sq., 9, Moscow, Russian Federation
2	Laboratory of Organic and Metal-organic Nitrogen-oxygen Systems (LOMONOS), N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prospect, 47, Moscow, Russian Federation
3	Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie gory, 1, str. 3, Moscow, Russian Federation

1,2-Oxazines possessing two weakly bonded heteroatoms in the ring represent an expeditious platform to implement ring editing strategies. Here, we report a process in which simultaneous swapping of both endocyclic heteroatoms (nitrogen and oxygen) in 1,2-oxazine N-oxides takes place under acid-mediated and photochemical conditions. This methodology provides general access to five-membered heterocycles, such as N-substituted pyrroles and thiophenes. DFT calculations suggest a common α-hydroxynitroso intermediate for both acid-mediated and photochemical processes, which arises through O-protonation or photocyclization of 1,2-oxazine N-oxides, followed by in situ hydrolysis.

Dvinyaninova T.Y. , Zhirov A.V. , Pospelov E.V. , Golovanov I.S. , Sukhorukov A.Y.
An N–O to N/S atom swapping process in 1,2-oxazine N -oxides to access pyrroles and thiophenes
Organic Chemistry Frontiers. 2026. V.13. N18. P.6091-6101. DOI: 10.1039/d6qo00597g WOS Scopus OpenAlex

Submitted:	Apr 30, 2026
Published online:	Jul 22, 2026

≡ Web of science:	WOS:001838176100001
≡ Scopus:	2-s2.0-105046339688
≡ OpenAlex:	W7170062281