On the scope of oxidation of tertiary amines: Meisenheimer rearrangements versus Cope elimination in 2-(cyanoethyl)-2-azanorbornanes

In this work, rearrangement reactions subsequent to the oxidation of tertiary amines were studied in 2-(cyanoethyl)-2-azanorbornane/ene systems. [1,2]- and [2,3]-Meisenheimer rearrangements, as well as the Cope elimination reaction, were observed with virtually complete selectivity. It was found tha...

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Published inORGANIC CHEMISTRY FRONTIERS Vol. 3; no. 12; pp. 1624 - 1634
Main Authors Sousa, Carlos A. D., Sampaio-Dias, Ivo E., Garcia-Mera, Xerardo, Lima, Carlos F. R. A. C., Rodriguez-Borges, Jose E.
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 01.01.2016
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
FUNCTIONALIZATION
ROUTE
ISOXAZOLIDINES
DIASTEREOSELECTIVE SYNTHESIS
INTERMEDIATE
AZA-DIELS-ALDER
CYCLOPENTADIENE
INHIBITORS
NONNATURAL CHIRAL AUXILIARY
DERIVATIVES
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Summary:In this work, rearrangement reactions subsequent to the oxidation of tertiary amines were studied in 2-(cyanoethyl)-2-azanorbornane/ene systems. [1,2]- and [2,3]-Meisenheimer rearrangements, as well as the Cope elimination reaction, were observed with virtually complete selectivity. It was found that 2-(cyanoethyl)-2-azanorbornanes afford N-hydroxylamines through Cope elimination reactions and 2-(cyanoethyl)-2-azanorbornenes are prone to Meisenheimer rearrangements. In addition, the endo/exo configuration of 2-azanorbornenes plays a key role in the Meisenheimer rearrangement outcome. All the synthesized compounds were fully characterized by NMR spectroscopy and HRMS.
Bibliography:FCT
ISSN:2052-4129
DOI:10.1039/c6qo00330c