581814-43-9Relevant articles and documents
An Unconventional Reaction of 2,2-Diazido Acylacetates with Amines
H?ring, Andreas P.,Biallas, Phillip,Kirsch, Stefan F.
supporting information, p. 1526 - 1539 (2017/04/01)
We have discovered that 2,2-diazido acylacetates, a class of compounds with essentially unknown reactivity, can be coupled to amines through a new strategy that does not involve any reagents. 2,2-Diazido acetate is the unconventional leaving group under carbon–carbon bond cleavage. This reaction leads to the construction of amide bonds, tolerates various functionalities and is performed equally well in numerous solvents under experimentally simple conditions. We also demonstrate that the isolation of the 2,2-diazido acylacetate compounds can be circumvented: Acylacetates were easily fragmented when treated with (Bu4N)N3 and iodine in the presence of an amine at room temperature. By using this method, a broad range of acylacetates with various structural motifs were directly transformed into amides.
Cleavage of 1,3-dicarbonyls through oxidative amidation
Biallas, Phillip,H?ring, Andreas P.,Kirsch, Stefan F.
supporting information, p. 3184 - 3187 (2017/04/21)
A mild and convenient protocol for the oxidative cleavage of 1,3-diketone compounds is described. Under metal-free conditions, the method converts the 1,3-dicarbonyls into amides when treated with (nBu4N)N3 and iodine in the presence of an amine at room temperature. Using this method, a range of 1,3-dicarbonyls with various structural motifs including sterically demanding substituents and ordinary functional groups were easily fragmented, and it is demonstrated that cyclic 1,3-dicarbonyls can be directly transformed into acyclic diamides through ring-opening. Initial mechanistic studies show that diazidation of the enol form is followed by nucleophilic substitution with the amine.
Identification of a new endogenous metabolite and the characterization of its protein interactions through an immobilization approach
Kalisiak, Jarostaw,Trauger, Sunia A.,Kalisiak, Ewa,Morita, Hirotoshi,Fokin, Valery V.,et al.
experimental part, p. 378 - 386 (2009/06/28)
The emerging field of global mass-based metabolomics provides a platformfor discovering unknown metabolites and their specific biochemical path ways. We report the identification of a new endogenous metabolite, N4-(N- acetylaminopropyl)spermidine and the use of a novel proteomics based method for the investigation of its protein interaction using metabolite immobilization on agarose beads. The metabolite was isolated from the organism Pyrococcus furiosus, and structurally characterized through an iterative process of synthesizing candidate molecules and comparative analysis using accurate mass LC-MS/MS. An approach developed for the selective preparation of N 1-acetylthermospermine, one ofthe possible structures of the unknown metabolite, provides a convenien t route to new polyamine derivatives through methylation on the N8 and N4 of the thermospermine scaffold. The biochemical role of the novel metabolite as well as that of two other polyamines: spermidine and agmatine is investigated through metabolite immobilization and incubation with native proteins. The identification of eleven proteins that uniquely bind with N4-(N-acetylaminopropyl)spermidine, provides information on the role of this novel metabolite in the native organism. Identified proteins included hypothetical ones such as PF0607 and PF1199, and those involved in translation, DNA synthesis and the urea cycle like translation initiation factor IF-2, 50S ribosomal proteinL14e, DNA-directed RNA polymerase, and ornithine carbamoyltransferase. The immobilization approach demonstrated here has the potential for appl ication to other newly discovered endogenous metabolites found through untargeted metabolomics, as a preliminary screen for generating a list ofproteins that could be further investigated for specific activity.
