SPACE STRUCTURE OF D-Orn²-CONTAINING ENKEPHALIN CYCLOANALOGUES IN DIMETHYLSULPHOXIDE SOLUTION

SHENDEROVICH M. D., SAULITIS J., BOBROVA I. V., PUCHINA A. V., ABISSOVA N. A., NIKIFOROVICH G. V., CHIPENS G. I.

Institute of Organic Synthesis, Academy of Sciences of the Latvian SSR, Riga

Abstract: The sterically acceptable structures of cyclo(2δ→5)[D-Orn², Pro5]- and cyclo(2δ→5)[D-Orn², Leu5]enkephalin (CE1 and CE2) consistent with NMR data including coupling constants, temperature dependencies of chemical shifts for amide protons and NOE values have been found by use of energy calculations in terms of rigid valence geometry and refined by the MM2 procedure. It has been shown that the major trans-iso-mer (with respect to Phe4-Pro5 bond) of CE1 in solution corresponds only to the FD*F*AA type of peptide backbone, and the minor cis-isomer of CE1 corresponds only to the FE*D*DF type. The less conformationally rigid CE2 analogue apparently exists in solution in the dynamic conformational equilibrium with preference of FD*C*AA type of the backbone structure. The obtained data on CE1 and CE2 space structures have been used for inter-pretating results of their biological testing.

Russian Journal of Bioorganic Chemistry 1990, 16 (1):21-33

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