Abstract
24-Membered ring pseudopeptides, cyclo[Gly-eXX-Gly]2 {eXX; N,N′-ethylene-bridged dipeptide, X = (S)-alanine(A), -leucine(L), -isoleucine(I), and -phenylalanine(F)} and cyclo[Sar-eXX-Gly]2 {X = (S)-A and -F} were prepared and their conformations were investigated by 1H and 13C NMR spectroscopy in dimethylsulfoxide-d6. It was found from NMR measurements that the major conformers ( ≥90% abundance) of the four cyclo[Gly-eXX-Gly]2 and major ones (≃70%) of the two cyclo[Sar-eXX Gly]2 have C2-symmetric structures, in which all peptide bonds of cyclo[Gly-eXX-Gly]2 (X = A, L, and I) and cyclo[Sar-eAA-Gly]2 are trans, while two Gly-eFF peptide bonds of cyclo[Gly-eFF-Gly]2 and two Sar-eFF ones of cyclo[Sar-eFF-Gly]2 are cis though the other peptide bonds are trans. 13C spin-lattice relaxation times (T1) of all macrocycles showed small contribution of segmental mobility to T1. The structures of cyclo[Gly-eAA-Gly]2 and cyclo[Sar-eAA-Gly]2 were optimized by molecular mechanics on the basis of NMR data.
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Kojima, Y., Goto, H., Miyake, H. et al. Conformations of 24-Membered Ring Pseudopeptides Containing N,N′-Ethylene-Bridged Dipeptides Constructed from (S)-Alanine, -Leucine, -Isoleucine, and -Phenylalanine. Polym J 26, 257–265 (1994). https://doi.org/10.1295/polymj.26.257
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DOI: https://doi.org/10.1295/polymj.26.257