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Enantiomer selection in the reaction of N-methyl-α-amino acid N-carboxyanhydride and 3-methyl-5-substituted hydantoin: A model reaction for the stereoselective polymerization of α-amino acid N-carboxyanhydride

✍ Scribed by Yutaka Hashimoto; Yukio Imanishi

Publisher
Wiley (John Wiley & Sons)
Year
1980
Tongue
English
Weight
677 KB
Volume
19
Category
Article
ISSN
0006-3525

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✦ Synopsis

Abstract

The addition reaction to N‐methyl‐(S)‐alanine or N‐methyl‐(S)‐phenylalanine N‐car‐boxyanhydride (NCA) of 3‐methyl‐5‐substituted hydantoin (HDT) catalyzed by a tertiary amine was investigated as a model reaction for the propagation reaction of NCA according to the activated‐NCA mechanism. Several activated HDTs having the (S)‐configuration of the asymmetric carbon atom were found to react more rapidly than their activated enantiomers. This experimental result indicates that the enantiomer selection by terminal‐unit control takes place in the propagation reaction according to the activated‐NCA mechanism in which an activated NCA is added to a terminal acylated NCA ring of the growing chain. The enantiomer excess of the HDT recovered from the reaction mixture of N‐methyl‐(S)‐phenylalanine NCA and racemic HDTs activated by a tertiary amine was determined. The extent of the enantiomer selection in the polymerization was found to be 3–10 times as large as that in the model reaction. From these results, it was concluded that the chirality of the penultimate unit, as well as that of the terminal NCA ring, plays an important role in determining the enantiomer selection in the NCA polymerization.

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