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

Autor:	Aleksandr O. Kokuev, Ivan S. Golovanov, Andrey A. Tabolin, Sema L. Ioffe, Alexey Yu. Sukhorukov, Valentin S. Dorokhov, Yulia A. Antonova, Yulia V. Nelyubina
Rok vydání:	2018
Předmět:	In situ 010405 organic chemistry Stereochemistry Chemistry Organic Chemistry Regioselectivity Total synthesis Sigmatropic reaction 010402 general chemistry Cleavage (embryo) 01 natural sciences 0104 chemical sciences Umpolung Acylation
Zdroj:	The Journal of Organic Chemistry. 83:11057-11066
ISSN:	1520-6904 0022-3263
DOI:	10.1021/acs.joc.8b01652
Popis:	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.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::57c687a5ea637f390c4b6ec098bb59af https://doi.org/10.1021/acs.joc.8b01652 Zobrazit plný text záznamu