Long-range chemical ligation from N→N acyl migrations in tryptophan peptides via cyclic transition states of 10- to 18-members.
Chemical ligations to form native peptides from N→N acyl migrations in Trp-containing peptides via 10- to 18-membered cyclic transition states are described. In this study, a statistical, predictive model that uses an extensive synthetic and computational approach to rationalize the chemical ligation is reported. N→N acyl migrations that form longer native peptides without the use of Cys/Ser/Tyr residues or an auxiliary group at the ligation site were achieved. The feasibility of these traceless chemical ligations is supported by the N-C bond distance in N-acyl isopeptides. The intramolecular nature of the chemical ligations is justified by using competitive experiments and theoretical calculations.
Department of Chemistry, University of Florida, Gainesville, FL 32611 (USA).
Suvendu
S
Biswas
Roger
R
Kayaleh
Girinath G
GG
Pillai
Christopher
C
Seon
Ian
I
Roberts
Vadim
V
Popov
Khalid A
KA
Alamry
Alan R
AR
Katritzky
D000215:Acylation; D008026:Ligation; D015394:Molecular Structure; D010455:Peptides / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D014364:Tryptophan / Q000031:analogs & derivatives / Q000737:chemistry*
D010455:Peptides; D014364:Tryptophan
acyl migration; chemical ligation; peptides; transition states; tryptophan