Preparation and reactivity of aminoacyl pyroglutamates. Facile synthesis of 10-membered-ring cyclic dipeptides derived from 1,4-diaminobutyric and glutamic acids.
A number of protected proline-containing dipeptides Boc-Xaa-Pro-OBu(t) were converted via epimerization-free oxidation with RuO4 to dipeptides with an internal pyroglutamic acid residue, Boc-Xaa-Glp-OBu(t). The latter were subjected to oxidative Hoffman-type rearrangement induced by PhI[OC(O)CF3]2 to give N-(aminoacyl)-pyroglutamates. The behavior of these derivatives under basic conditions was studied, and for two such a derivatives an aminoacyl incorporation reaction was observed, producing otherwise poorly accessible 10-membered-ring dilactams derived from 1,4-diaminobutyric and glutamic acids in practicable yields.
Chulin
A N
AN
Branch of Shemyakin & Ovchinnikov Institute of Bioorganic Chemistry, Pushchino, Moscow Region, Russia.
Rodionov
I L
IL
Baidakova
L K
LK
Rodionova
L N
LN
Balashova
T A
TA
Ivanov
V T
VT
D049148:Aminoacylation; D000613:Aminobutyrates / Q000737:chemistry*; D018698:Glutamic Acid / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009952:Ornithine / Q000737:chemistry; D010084:Oxidation-Reduction; D010456:Peptides, Cyclic / Q000138:chemical synthesis* / Q000737:chemistry*; D011761:Pyrrolidonecarboxylic Acid / Q000737:chemistry
D000613:Aminobutyrates; D010456:Peptides, Cyclic; D018698:Glutamic Acid; D009952:Ornithine; D011761:Pyrrolidonecarboxylic Acid