Back to Search Start Over

Stereoselective oxidation of alkanes with m-CPBA as an oxidant and cobalt complex with isoindole-based ligands as catalysts

Authors :
Maximilian N. Kopylovich
Dmytro S. Nesterov
Oksana V. Nesterova
Source :
RSC Advances. 6:93756-93767
Publication Year :
2016
Publisher :
Royal Society of Chemistry (RSC), 2016.

Abstract

Two complexes with isoindole-core ligands of general formula [M{C6H4C(NH2)NC(ONCMe2)2}2](NO3)2 (M = Co for 1 and M = Ni for 2) were studied as catalysts for the mild stereoselective alkane oxidation with m-chloroperbenzoic acid (m-CPBA) as an oxidant and cis-1,2-dimethylcyclohexane (cis-1,2-DMCH) as a main model substrate. Complex 1 disclosed a pronounced activity, with high retention of stereoconfiguration of substrates (>98% for cis-1,2-DMCH) and highest cis/trans ratio of tertiary alcohols (products) of 56, under mild conditions. The best achieved yields of tertiary cis-alcohols were of 13.7 and 50.5%, based on the substrate (cis-1,2-DMCH) and the oxidant (m-CPBA) respectively. Kinetic experiments, high bond and stereoselectivity parameters, kinetic isotope effect of 7.2(2) in the oxidation of cyclohexane, and incorporation of 18O from H218O support the involvement of CoIVO high-valent metal–oxo intermediates as main C–H attacking species.

Details

ISSN :
20462069
Volume :
6
Database :
OpenAIRE
Journal :
RSC Advances
Accession number :
edsair.doi...........0008942ac20c8b5ca66d9262f5abb0ec
Full Text :
https://doi.org/10.1039/c6ra14382b