5467-51-6Relevant articles and documents
Sterically Demanding Oxidative Amidation of α-Substituted Malononitriles with Amines Using O2
Li, Jing,Lear, Martin J.,Hayashi, Yujiro
supporting information, p. 9060 - 9064 (2016/07/26)
An efficient amidation method between readily available 1,1-dicyanoalkanes and either chiral or nonchiral amines was realized simply with molecular oxygen and a carbonate base. This oxidative protocol can be applied to both sterically and electronically challenging substrates in a highly chemoselective, practical, and rapid manner. The use of cyclopropyl and thioether substrates support the radical formation of α-peroxy malononitrile species, which can cyclize to dioxiranes that can monooxygenate malononitrile α-carbanions to afford activated acyl cyanides capable of reacting with amine nucleophiles.
Umpolung reactivity in amide and peptide synthesis
Shen, Bo,Makley, Dawn M.,Johnston, Jeffrey N.
experimental part, p. 1027 - 1032 (2011/08/06)
The amide bond is one of natureg€s most common functional and structural elements, as the backbones of all natural peptides and proteins are composed of amide bonds. Amides are also present in many therapeutic small molecules. The construction of amide bonds using available methods relies principally on dehydrative approaches, although oxidative and radical-based methods are representative alternatives. In nearly every example, carbon and nitrogen bear electrophilic and nucleophilic character, respectively, during the carbong€"nitrogen bond-forming step. Here we show that activation of amines and nitroalkanes with an electrophilic iodine source can lead directly to amide products. Preliminary observations support a mechanism in which the polarities of the two reactants are reversed (German, umpolung) during carbong€"nitrogen bond formation relative to traditional approaches. The use of nitroalkanes as acyl anion equivalents provides a conceptually innovative approach to amide and peptide synthesis, and one that might ultimately provide for efficient peptide synthesis that is fully reliant on enantioselective methods.
Resonance Raman spectroscopic evidence for an intramolecular interaction involving th amide and dithioester groups of N-acyl glycine ethyl dithioesters
Storer, A. C.,Ozaki, Y.,Carey, P. R.
, p. 199 - 209 (2007/10/02)
The synthesis and resonance Raman spectra of several new N-acyl glycine etyl dithioesters RC(=O)NHCH2C(=S)SR are reported.The resonance Raman spectra of these compounds contain at least two peaks in the "C=S stretching region" between 1050 and 1200 cmsup
