Reductive Deletion of Endocyclic Oxygen Atom in 1,2‐Oxazine N ‐Oxides to Access N ‐Hydroxypyrrolidines

Reductive Deletion of Endocyclic Oxygen Atom in 1,2‐Oxazine N ‐Oxides to Access N ‐Hydroxypyrrolidines Full article

Journal

European Journal of Organic Chemistry
ISSN: 1434-193X , E-ISSN: 1099-0690

Output data

Year: 2026, Article number : e70863, Pages count : DOI: 10.1002/ejoc.70863

Authors

Pospelov Evgeny V. ^1,2 , Zharov Nikolai P. ^3,2 , Sukhorukov Alexey Yu. ²

Affiliations

1	Department of Chemistry Higher School of Economics National Research University Moscow Russia
2	Laboratory of Organic and Metal‐Organic Nitrogen‐Oxygen Systems (LOMONOS) N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences Moscow Russia
3	Department of Chemistry M. V. Lomonosov Moscow State University Moscow Russia

Single‐atom ring‐editing strategies have emerged as a powerful tool for the diversification of molecular libraries through the remodeling of key heterocyclic scaffolds. The 1,2‐oxazine core represents an ideal platform for implementing single heteroatom deletion/swapping strategies, which lead to five‐membered O‐ or N‐heterocycles with varying levels of saturation. Here, we introduce a novel reductive ring contraction of 1,2‐oxazine N‐oxides that achieves the formal deletion of the endocyclic oxygen atom, delivering synthetically valuable N‐hydroxypyrrolidines. This process operates under mild reductive conditions with the NaBH3CN/TsOH system via an unprecedented multistep ring opening/ring reconstruction sequence. The introduction of a recyclable chiral auxiliary enables a practical asymmetric variant, providing a route to enantioenriched N‐hydroxypyrrolidines.

Pospelov E.V. , Zharov N.P. , Sukhorukov A.Y.
Reductive Deletion of Endocyclic Oxygen Atom in 1,2‐Oxazine N ‐Oxides to Access N ‐Hydroxypyrrolidines
European Journal of Organic Chemistry. 2026. e70863 . DOI: 10.1002/ejoc.70863 WOS Scopus OpenAlex

Submitted:	Jul 23, 2026
Accepted:	Sep 11, 2026
Published online:	Sep 26, 2026

≡ Web of science:	WOS:001885308400001
≡ Scopus:	2-s2.0-105051526583
≡ OpenAlex:	W7214475943