Tandem 1,3-Dipolar Cycloaddition/Rearrangement of Nitronates with Cyclooctyne for the Diastereoselective Synthesis of Spiroaziridine Derivatives

Tandem 1,3-Dipolar Cycloaddition/Rearrangement of Nitronates with Cyclooctyne for the Diastereoselective Synthesis of Spiroaziridine Derivatives Full article

Journal

Organic Letters
ISSN: 1523-7060 , E-ISSN: 1523-7052

Output data

Year: 2026, Volume: 28, Number: 13, Pages: 4061-4066 Pages count : 6 DOI: 10.1021/acs.orglett.6c00553

Authors

Maksakova Polina I. ^1,2 , Malykhin Roman S. ² , Lukoyanov Alexander A. ² , Lesnikov Vladislav K. ² , Tabolin Andrey A. ²

Affiliations

1	Higher Chemical College, D. Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, Moscow 125047, Russian Federation
2	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prosp. 47, Moscow 119334, Russian Federation

The 1,3-dipolar cycloaddition of cyclic nitronates (5,6-dihydro-4H-1,2-oxazine N-oxides) with cyclooctyne affords oxazine-annulated spiroaziridine derivatives in mild conditions with high yields and diastereoselectivity via consecutive strain-promoted [3 + 2]-cycloaddition/ring contraction. Isoxazoline N-oxides and silyl nitronates also react smoothly, albeit with a lower diastereoselectivity. DFT calculations reveal key features, such as half-boat conformation of the oxazine ring during cycloaddition, and control of the stereoselectivity during ring contraction by an anomeric effect in the O–N–O moiety.

Maksakova P.I. , Malykhin R.S. , Lukoyanov A.A. , Lesnikov V.K. , Tabolin A.A.
Tandem 1,3-Dipolar Cycloaddition/Rearrangement of Nitronates with Cyclooctyne for the Diastereoselective Synthesis of Spiroaziridine Derivatives
Organic Letters. 2026. V.28. N13. P.4061-4066. DOI: 10.1021/acs.orglett.6c00553 WOS Scopus OpenAlex

Submitted:	Feb 3, 2026
Accepted:	Mar 19, 2026
Published print:	Mar 23, 2026
Published online:	Apr 3, 2026

≡ Web of science:	WOS:001722398800001
≡ Scopus:	2-s2.0-105034794746
≡ OpenAlex:	W7140197872