1455-99-8Relevant articles and documents
Metal free amide synthesis via carbon-carbon bond cleavage
Zhu, Chunyin,Wei, Wei,Du, Peng,Wan, Xiaobing
, p. 9615 - 9620 (2014)
A metal-free oxidative coupling of methyl ketones and primary amines to amides has been developed. The reaction tolerates a variety of functional groups, and is operationally simple. The reaction is proposed to go through a radical pathway to form the triiodomethyl ketone intermediate and the amide is formed by the nucleophilic attack of amine on triiodomethyl ketone carbonyl.
Visible Light-Driven Efficient Synthesis of Amides from Alcohols using Cu?N?TiO2 Heterogeneous Photocatalyst
Singha, Krishnadipti,Ghosh, Subhash Chandra,Panda, Asit Baran
, p. 657 - 662 (2021/02/02)
Amides were synthesized from alcohols and amines in high yields using an in situ generated active ester of N-hydroxyimide with our developed Cu?N?TiO2 catalyst at room temperature using oxygen as a sole oxidant under visible light. The catalyst can be easily prepared, robust, and recycled four times without a considerable change in catalytic activity. This developed protocol applies to a wide substrate scope and has good functional group tolerance. The application of this amidation reaction has been successfully demonstrated for the synthesis of moclobemide, an antidepressant drug, and an analog of the itopride drug on a gram scale.
A CO2-Catalyzed Transamidation Reaction
Yang, Yang,Liu, Jian,Kamounah, Fadhil S.,Ciancaleoni, Gianluca,Lee, Ji-Woong
, p. 16867 - 16881 (2021/11/18)
Transamidation reactions are often mediated by reactive substrates in the presence of overstoichiometric activating reagents and/or transition metal catalysts. Here we report the use of CO2as a traceless catalyst: in the presence of catalytic amounts of CO2, transamidation reactions were accelerated with primary, secondary, and tertiary amide donors. Various amine nucleophiles including amino acid derivatives were tolerated, showcasing the utility of transamidation in peptide modification and polymer degradation (e.g., Nylon-6,6). In particular,N,O-dimethylhydroxyl amides (Weinreb amides) displayed a distinct reactivity in the CO2-catalyzed transamidation versus a N2atmosphere. Comparative Hammett studies and kinetic analysis were conducted to elucidate the catalytic activation mechanism of molecular CO2, which was supported by DFT calculations. We attributed the positive effect of CO2in the transamidation reaction to the stabilization of tetrahedral intermediates by covalent binding to the electrophilic CO2
Metal-Free C-N or C-C Bond Cleavages of α-Azido Ketones: An Oxidative-Amidation Strategy for the Synthesis of α-Ketothioamides and Amides
Yu, Pei,Wang, Yuwei,Zeng, Zhigang,Chen, Yunfeng
, p. 14883 - 14891 (2019/11/11)
A novel metal-free oxidative-amidation strategy for the synthesis of α-ketothioamides and amides from α-azido ketones was developed. The C-H bond thionation of α-azido ketones with elemental sulfur could form α-ketothioacyl azide, which was then nucleophilically attacked by amines, causing the cleavage of the C-N bond to afford α-ketothioamides, while amides could be formed with the release of nitrogen gas and cyano anion in the presence of PhI(OAc)2 by selective C-C bond cleavage.