Construction of Saturated Oxazolo[3,2-b][1,2]oxazines via Tandem [3+2]-Cycloaddition/[1,3]-Rearrangement of Cyclic Nitronates and Ketenes

Construction of Saturated Oxazolo[3,2-b][1,2]oxazines via Tandem [3+2]-Cycloaddition/[1,3]-Rearrangement of Cyclic Nitronates and Ketenes Full article

Journal

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

Output data

Year: 2021, Volume: 86, Number: 23, Pages: 16337-16348 Pages count : 12 DOI: 10.1021/acs.joc.1c01744

Authors

Malykhin Roman S. ^1,2 , Golovanov Ivan S. ² , Nelyubina Yulia V. ³ , Ioffe Sema L. ² , Sukhorukov Alexey Yu. ²

Affiliations

1	Department of Chemistry, M. V. Lomonosov Moscow State University, 119991, Leninskie gory, 1, str. 3, Moscow, Russian Federation
2	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991, Leninsky prospect, 47, Moscow, Russian Federation
3	A. N. Nesmeyanov Institute of Organoelement Compounds, 119991, Vavilov str. 28, Moscow, Russian Federation

Reaction of six-membered cyclic nitronates with disubstituted ketenes affords hitherto unknown saturated oxazolo[3,2-b][1,2]oxazines possessing up to four contiguous stereogenic centers. The process involves a tandem of [3+2]-cycloaddition across the C═O bond of ketene, followed by a spontaneous [1,3]-rearrangement of transient vinylidene-substituted bicyclic nitrosoacetals. DFT calculations of the mechanism suggest that the [1,3]-O,C-shift proceeds through a recyclization of a biradical intermediate formed by an unusually mild homolytic cleavage of the N–O bond. The resulting products can be utilized as precursors of other fused 1,2-oxazines derivatives, in particular 1,2-oxazino-1,2,4-triazin-3-ones.

Malykhin R.S. , Golovanov I.S. , Nelyubina Y.V. , Ioffe S.L. , Sukhorukov A.Y.
Construction of Saturated Oxazolo[3,2-b][1,2]oxazines via Tandem [3+2]-Cycloaddition/[1,3]-Rearrangement of Cyclic Nitronates and Ketenes
Journal of Organic Chemistry. 2021. V.86. N23. P.16337-16348. DOI: 10.1021/acs.joc.1c01744 WOS Scopus OpenAlex

Web of science:	WOS:000752848600012
Scopus:	2-s2.0-85120043890
OpenAlex:	W3214645077

DB	Citing
OpenAlex	6
Scopus	6
Web of science	5