Abstract
Chiral ester cleavage by achiral hydroxamic acids was investigated in the presence of chiral matrix micelles formed from amphiphiles with poly-l-lysine-head groups. The results are summarized as follows. (1) The enantioselectivity was not observed in the alkaline hydrolysis in chiral micelles only. This matrix possesses no selectivity. When an achiral hydroxamic acid was added to the system, selectivity was induced. (2) The direction of selectivity is reversed by the conformational change of the secondary structure formed by the peptide moiety of matrix micelles. L-Selectivity in the random coil and D-selectivity in the α-helix condition were observed. (3) The degree of selectivity is dependent on the chemical structure of hydroxamic acid; for example, an N–H type hydroxamic acid gives higher selectivity than an N-methyl type one. Thus, it is supposed that enantioselectivity is introduced by the chiral interaction between chiral micelles and achiral nucleophiles, in which the conformation of polypeptide moiety plays an important role.
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Ihara, H., Ide, T., Hotta, O. et al. Amphiphiles with Polypeptide-Head Groups III. Regulation of Enantioseiectivity in Micellar Hydrolysis. Polym J 18, 463–469 (1986). https://doi.org/10.1295/polymj.18.463
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DOI: https://doi.org/10.1295/polymj.18.463
