jo9b02003_si_002.pdf (7.53 MB)
Redox Property of Enamines
journal contribution
posted on 2019-09-09, 14:38 authored by Yao Li, Dehong Wang, Long Zhang, Sanzhong LuoEnamines are electron-rich
compounds bearing intriguing redox properties.
Herein, a series of secondary enamines condensed from primary amine
and β-ketocarbonyls were synthesized and their electrochemical
oxidation properties were systematically studied by cyclic voltammetry.
Furthermore, theoretical calculation of oxidation potentials of enamines,
particularly those catalytic intermediates, was also conducted to
further broaden the scope investigated. Possible structural factors
on oxidation and the nature of the resulted radical cation intermediates
were revealed and discussed. Correlation of redox potentials with
molecular properties such as highest occupied molecular orbital energies
and natural population analysis charge were explored, and there appears
no simple linear correlation. On the other hand, a good correlation
with Mayr’s nucleophilicity parameter N was
noted among a range of catalytically relevant enamines. Spin population
analysis disclosed that enamine radical cations mainly exhibit the
carbon-center free radical feature. Taking experimental and computation
data together, a comprehensive picture about the redox property of
enamines is presented, which would provide guidance in the development
of oxidative enamine catalysis and transformations.
History
Usage metrics
Categories
Keywords
cation intermediatesoxidative enamine catalysisβ- ketocarbonylsredox propertieselectron-rich compoundsoxidation potentialscyclic voltammetrycomputation dataredox potentialselectrochemical oxidation propertiesSpin population analysispopulation analysis chargeEnamines EnaminesRedox Propertyredox property
Licence
Exports
RefWorks
BibTeX
Ref. manager
Endnote
DataCite
NLM
DC