127223-95-4Relevant articles and documents
Redox Property of Enamines
Li, Yao,Wang, Dehong,Zhang, Long,Luo, Sanzhong
, p. 12071 - 12090 (2019/10/11)
Enamines 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.
One-pot formation of aza-enolates from secondary amines and condensation to esters and alkyl bromides
Chevalley, Alice,Férézou, Jean-Pierre
experimental part, p. 5882 - 5889 (2012/09/11)
Starting from commercial secondary amines, a one-pot procedure allows a direct access to enaminones through a one-pot deprotonation/oxidation/in situ re-deprotonation/acylation sequence without intermediate isolation of the intermediate Schiff base or its corresponding enamine tautomer. An alternative one-pot sequence involving a similar oxidation step followed by one or two alkylation steps yields, after acidic work-up, functionalized ketones directly from the parent amine. This process has been applied to an expeditious synthesis of the male aggregation pheromone of the cereal leaf beetle Oulema melanopus.
O-N, S-N AND N-N EXCHANGE REACTIONS AT OLEFINIC CARBON ATOMS: FACILE SYNTHETIC METHOD FOR β-TRIFLUOROACETYLVINYLAMINES
Hojo, Masaru,Masuda, Ryoichi,Okada, Etsuji,Sakaguchi, Syuhei,Narumiya, Hitoshi,Morimoto, Katsushi
, p. 6173 - 6176 (2007/10/02)
β-Trifluoroacetylvinyl ethers 1 and sulfides 2 react easily with various amines at room temperature to give β-trifluoroacetylvinylamines 3 in excellent yields.This O-N and S-N exchange reaction can be extended to N-N exchange reaction.
