54385-24-9Relevant academic research and scientific papers
Selective α-Oxyamination and Hydroxylation of Aliphatic Amides
Li, Xinwei,Lin, Fengguirong,Huang, Kaimeng,Wei, Jialiang,Li, Xinyao,Wang, Xiaoyang,Geng, Xiaoyu,Jiao, Ning
supporting information, p. 12307 - 12311 (2017/09/11)
Compared to the α-functionalization of aldehydes, ketones, even esters, the direct α-modification of amides is still a challenge because of the low acidity of α-CH groups. The α-functionalization of N?H (primary and secondary) amides, containing both an unactived α-C?H bond and a competitively active N?H bond, remains elusive. Shown herein is the general and efficient oxidative α-oxyamination and hydroxylation of aliphatic amides including secondary N?H amides. This transition-metal-free chemistry with high chemoselectivity provides an efficient approach to α-hydroxy amides. This oxidative protocol significantly enables the selective functionalization of inert α-C?H bonds with the complete preservation of active N?H bond.
The mechanism of electrochemical reduction of N-haloamides in acetonitrile: trapping of intermediate amide anions and father-son protonation
Berube, Denis,Lessard, Jean
, p. 1127 - 1142 (2007/10/02)
The electrochemical reduction of N-haloamides (ZCONRX) in acetonitrile involves two consecutive one-electron transfers and generates the amide anions.Attempts to trap the intermediate amidyl radical resulting from first electron transfer were unssuccesful.In the case of the N-halo-N-hydroamides (R=H), the amide anion formed at the electrode abstracts a proton from an incoming N-halo-N-hydroamide molecule to give the parent amide and the conjugate base of the N-haloamide (father-son protonation).Thus, half of the N-halo-N-hydroamide reaching the electrode is reduced, the other half being converted to its conjugate base.In acetonitrile-LiClO4 (0.2 M) containing 0.2percent water, the conjugate base is reducible and polarograms therefore show two waves (irreversible and diffusion controlled) of equivalent intensities due respectively to the reduction of the N-halo-N-hydroamide and to the reduction of its conjugate base.In the case of the N-chloro-N-alkyl(aryl)amides (X=Cl, R=alkyl or aryl), the amide anion abstracts a proton from the medium to give the parent amide and anionic species that react with the starting N-chloroamide regenerating the amide anion.Hence, the coulometric results are low (0.5 F/mol).However, in the presence of acetic acid, the reduction consumes 2 F/mol as expected.The N-alkylamide anion has been trapped by N-alkylation and N-acylation.The voltammograms of N-chloro-N-alkyl(aryl)amides show multiple waves on mercury and platinum due to passivation-adsorption phenomena but a single wave on vitreous carbon.
