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Chemistry. 2014 Jun 23;20(26):8189-98. doi: 10.1002/chem.201400125. Epub 2014 May 13.

Long-range chemical ligation from N→N acyl migrations in tryptophan peptides via cyclic transition states of 10- to 18-members.

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Department of Chemistry, University of Florida, Gainesville, FL 32611 (USA).


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.


acyl migration; chemical ligation; peptides; transition states; tryptophan

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