3251-08-9Relevant articles and documents
Synthesis of functionalized glutamine- and asparagine-type peptoids-scope and limitations
Cardenal, Carmen,Vollrath, Sidonie B. L.,Schepers, Ute,Br?se, Stefan
, p. 2237 - 2248 (2013/02/23)
N-Alkylated glycine oligomers ('peptoids') can serve as potent peptidomimetic systems. Installing different functional groups can often be a challenge, and minimizes yields and purities. Here, we describe the synthesis of different amide-containing submonomers which were obtained as free bases, as well as their incorporation into peptoids. By using the free amines, the coupling results on solid support could be improved, and various functionalized peptoids were prepared. Additionally, an interesting dimerization side reaction leading to cross-linked peptoids was observed during synthesis.
Mapping of the active site of rat kidney γ-glutamyl transpeptidase using activated esters and their amide derivatives
Castonguay, Roselyne,Lherbet, Christian,Keillor, Jeffrey W.
, p. 4185 - 4191 (2007/10/03)
The enzyme γ-glutamyl transpeptidase (GGT), implicated in many physiological processes, catalyses the transfer of a γ-glutamyl from a donor substrate to an acyl acceptor substrate, usually an amino acid or a peptide. In order to investigate which moieties of the donor substrate are necessary for recognition by GGT, the structure of the well-recognized substrate L-γ-glutamyl-p-nitroanilide was modified. Several activated esters and their amide derivatives were synthesized and used as substrates. Kinetic (Km and Vmax) and inhibition constants (Ki) were measured and reveal that almost the entire γ-glutamyl moiety is necessary for recognition in the binding site of the donor substrate. The implied presence of certain complementary amino acids in this substrate binding site will allow the more rational design of various substrate analogues and inhibitors.
A Critical Test of the Theory of Stereoelectronic Control
Perrin, Charles L.,Arrhenius, Gloria Meichia L.
, p. 2839 - 2842 (2007/10/02)
According to Deslongchamps' theory of stereoelectronic control, preferential cleavage of a tetrahedral intermediate occurs when there are two lone pairs antiperiplanar to the leaving group.However, it is concluded that the experimental evidence is ambiguous, because it requires an unreasonable assumption regarding rates of ring inversion and because there is a simpler explanation for the observations.Nevertheless, the theory is a plausible one, deserving unambiguous evidence to support it.The hydrolysis of cyclic amidines (4), via the hemiorthoamide (5), can provide a suitable test.It is observed that 2-amino-1-pyrroline (4, n = 5) and "2-iminopiperidine" (4, n = 6) hydrolyze in base solely to the amino amide (6), which is converted under the reaction conditions to the thermodynamically more stable lactam (7).This result is the first unambiguous evidence for stereoelectronic control, and it also shows that cleavage of the intermediate (5) is fast compared to nitrogen inversion.