13540-95-9Relevant articles and documents
Metal-Free Thermal Activation of Molecular Oxygen Enabled Direct α-CH2-Oxygenation of Free Amines
Ghosh, Santanu,Jana, Chandan K.
, p. 260 - 266 (2018/02/19)
Direct oxidation of α-CH2 group of free amines is hard to achieve due to the higher reactivity of amine moiety. Therefore, oxidation of amines involves the use of sophisticated metallic reagents/catalyst in the presence or absence of hazardous oxidants under sensitive reaction conditions. A novel method for direct C-H oxygenation of aliphatic amines through a metal-free activation of molecular oxygen has been developed. Both activated and unactivated free amines were oxygenated efficiently to provide a wide variety of amides (primary, secondary) and lactams under operationally simple conditions without the aid of metallic reagents and toxic oxidants. The method has been applied to the synthesis of highly functionalized amide-containing medicinal drugs, such as O-Me-alibendol and -buclosamide.
Aromatic aldehyde-catalyzed gas-phase decarboxylation of amino acid anion via imine intermediate: An experimental and theoretical study
Xiang, Zhang
, p. 149 - 156 (2013/10/22)
It is generally appreciated that carbonyl compound can promote the decarboxylation of the amino acid. In this paper, we have performed the experimental and theoretical investigation into the gas-phase decarboxylation of the amino acid anion catalyzed by the aromatic aldehyde via the imine intermediate on the basis of the tandem mass spectrometry (MS/MS) technique and density functional theory (DFT) calculation. The results show that the aromatic aldehyde can achieve a remarkable catalytic effect. Moreover, the catalytic mechanism varies according to the type of amino acid: (i) The decarboxylation of α-amino acid anion is determined by the direct dissociation of the C-C bond adjacent to the carboxylate, for the resulting carbanion can be well stabilized by the conjugation between α-carbon, C=N bond and benzene ring. (ii) The decarboxylation of non-α-amino acid anion proceeds via a SN2-like transition state, in which the dissociation of the C-C bond adjacent to the carboxylate and attacking of the resulting carbanion to the C=N bond or benzene ring take place at the same time. Specifically, for β-alanine, the resulting carbanion preferentially attacks the benzene ring leading to the benzene anion, because attacking the C=N bond in the decarboxylation can produce the unstable three or four-membered ring anion. For the other non-α-amino acid anion, the C=N bond preferentially participates in the decarboxylation, which leads to the pediocratic nitrogen anion.
Synthesis of 2-alkyl-1-aryl-1,2-dihydrochromeno[2,3-c]pyrrole-3,9-dione derivatives
Vydzhak,Panchishin, S. Ya.
experimental part, p. 2391 - 2397 (2009/05/30)
A preparative procedure for the synthesis of 2-alkyl-1-aryl-1,2- dihydrochromeno[2,3-c]pyrrole-3,9-diones from methyl 4-(o-hydroxyphenyl)-2,4- dioxobutanoate, aromatic aldehyde, and aliphatic amine is described.
