1361044-54-3Relevant academic research and scientific papers
The mechanism of the α-ketoacid-hydroxylamine amide-forming ligation
Pusterla, Ivano,Bode, Jeffrey W.
, p. 513 - 516 (2012/03/22)
Three-ring circus! Surprisingly complex molecular acrobatics are observed in the mechanism of the α-ketoacid-hydroxylamine amide-forming ligation reaction. Although this remarkable reaction can already be used for the chemoselective union of large, unprotected peptide fragments the elucidated mechanism provides important clues to extending its application to larger and more complex biological targets. Copyright
Discovery of competing anaerobic and aerobic pathways in umpolung amide synthesis allows for site-selective amide18O-labeling
Shackleford, Jessica P.,Shen, Bo,Johnston, Jeffrey N.
scheme or table, p. 44 - 46 (2012/03/27)
The mechanism of umpolung amide synthesis was probed by interrogating potential sources for the oxygen of the product amide carbonyl that emanates from the α-bromo nitroalkane substrate. Using a series of 18O-labeled substrates and reagents, evidence is gathered to advance two pathways from the putative tetrahedral intermediate. Under anaerobic conditions, a nitro-nitrite isomerization delivers the amide oxygen from nitro oxygen. The same homolytic nitro-carbon fragmentation can be diverted by capture of the carbon radical intermediate with oxygen gas (O2) to deliver the amide oxygen from O2. This understanding was used to develop a straightforward protocol for the preparation of 18O-labeled amides in peptides by simply performing the umpolung amide synthesis reaction under an atmosphere of 18O2.
