Interrupted Nef Reaction of Cyclic Nitronates: Diastereoselective Access to Densely Substituted α-Chloronitroso Compounds

Interrupted Nef Reaction of Cyclic Nitronates: Diastereoselective Access to Densely Substituted α-Chloronitroso Compounds Full article

Journal

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

Output data

Year: 2022, Volume: 87, Number: 24, Pages: 16617-16631 Pages count : 15 DOI: 10.1021/acs.joc.2c02281

Authors

Malykhin Roman S ^1,2 , Boyko Yaroslav D ³ , Nelyubina Yulia V ⁴ , 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	UIUC: Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, United States
4	A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991, Vavilova str. 28, Moscow, Russian Federation

The reaction of cyclic nitronic esters (isoxazoline- and 5,6-dihydro-4H-1,2-oxazine-N-oxides) with hydrochloric acid affords geminal chloronitroso compounds bearing a distant hydroxyl group. The reaction is usually diastereoselective, and in some cases stereodivergent formation of isomers at different temperatures is observed. The discovered process represents the first example of an interrupted Nef reaction of nitronic esters. DFT calculations support the initial formation of N,N-bis(oxy)iminium cations (key intermediates in the Nef reaction), which are intercepted by the chloride anion followed by ring opening. The synthetic utility of the resulting functionalized chloronitroso compounds in the Diels–Alder reaction with cyclopentadiene was demonstrated.

Malykhin R.S. , Boyko Y.D. , Nelyubina Y.V. , Ioffe S.L. , Sukhorukov A.Y.
Interrupted Nef Reaction of Cyclic Nitronates: Diastereoselective Access to Densely Substituted α-Chloronitroso Compounds
Journal of Organic Chemistry. 2022. V.87. N24. P.16617-16631. DOI: 10.1021/acs.joc.2c02281 WOS Scopus OpenAlex

Web of science:	WOS:000899990400001
Scopus:	2-s2.0-85143548966
OpenAlex:	W4310641972

DB	Citing
OpenAlex	10
Scopus	9
Web of science	9