Acylation of Nitronates: [3,3]-Sigmatropic Rearrangement of in Situ Generated N-Acyloxy, N-oxyenamines

Aleksandr O Kokuev; Yulia A Antonova; Valentin S Dorokhov; Ivan S Golovanov; Yulia V Nelyubina; Andrey A Tabolin; Alexey Yu Sukhorukov; Sema L Ioffe

doi:10.1021/acs.joc.8b01652

Acylation of Nitronates: [3,3]-Sigmatropic Rearrangement of in Situ Generated N-Acyloxy, N-oxyenamines

J Org Chem. 2018 Sep 21;83(18):11057-11066. doi: 10.1021/acs.joc.8b01652. Epub 2018 Aug 16.

Authors

Aleksandr O Kokuev^{1

2}, Yulia A Antonova^{1

3}, Valentin S Dorokhov^{1

2}, Ivan S Golovanov¹, Yulia V Nelyubina⁴, Andrey A Tabolin¹, Alexey Yu Sukhorukov¹, Sema L Ioffe¹

Affiliations

¹ N. D. Zelinsky Institute of Organic Chemistry , Russian Academy of Sciences , Leninsky prospect 47 , 119991 , Moscow , Russian Federation.
² Higher Chemical College , D. I. Mendeleev University of Chemical Technology of Russia , Miusskaya sq. 9 , 125047 , Moscow , Russian Federation.
³ Department of Chemistry , M. V. Lomonosov Moscow State University , Leninskie gory 1 , 119991 , Moscow , Russian Federation.
⁴ A. N. Nesmeyanov Institute of Organoelement Compounds , Russian Academy of Sciences , Vavilov str. 28 , 119991 , Moscow , Russian Federation.

PMID: 30067029
DOI: 10.1021/acs.joc.8b01652

Abstract

Acylation of nitronates affords α-acyloxyoxime derivatives via an umpolung functionalization of the α-position. This transformation involves generation of hitherto unknown N-acyloxy, N-oxyenamines and their fast [3,3]-sigmatropic rearrangement driven by the cleavage of the weak N-O bond. The reaction has a broad scope, and it is regioselective in the case of nitronates possessing nonsymmetrically substituted α-positions. Application to the formal total synthesis of clausenamide and cis-clausenamide is presented.