165337-20-2Relevant academic research and scientific papers
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.
Visible Light Promoted β-C—H Alkylation of β-Ketocarbonyls via a β-Enaminyl Radical Intermediate
Wang, Dehong,Zhang, Long,Luo, Sanzhong
, p. 311 - 320 (2018/02/21)
A 5πe carbonyl activation mode is reported on the basis of photo-induced single-electron-transfer (SET) oxidation of a secondary enamine. The resultant β-enaminyl radical intermediate was trapped by a wide range of Michael acceptors, producing β-alkylation products of β-ketocarbonyls in a highly efficient manner.
Efficient one-pot synthesis of cyclic β-enaminoamides by thermal Wolff rearrangement of cyclic 2-diazo-1,3-dicarbonyls and conversion to uracil derivatives
Neupane, Pratik,Li, Xin,Jung, Jae Hak,Lee, Yong Rok,Kim, Sung Hong
, p. 2496 - 2508 (2012/04/23)
This paper describes simple and efficient approaches for the preparation of β-enaminoamides through thermal Wolff rearrangement of cyclic diazodicarbonyls followed by trapping with various amines. The synthesized β-enaminoamides were readily converted into uracil derivatives.
