Graduate Thesis Or Dissertation
 

Biosynthesis of blasticidin S : mechanistic and stereochemical investigations

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  • Feeding of [3-¹³C, 2-¹⁵N]arginine, 38a, unequivocally established that the β- arginine moiety of blasticidin S, 1, was formed from α-arginine by an intramolecular migration of the α-amino group to the β- position. Further feedings using chirally deuteriated arginines 38e and 38f revealed that the aminomutase process occurred with inversion of configuration at C-3 of arginine and the 3-pro-R hydrogen was involved in the migration from C-3 to C-2. Efforts to assign the absolute stereochemistry of alcohols 45a and 45b, intermediates in the synthesis of 38e and 38f, led to the discovery that the Gerlach- Zagalak analysis of their corresponding (-)-camphanates had yielded results contrary to the well established empirical rule, the first time this had been observed. Synthesis and feeding of labeled β- arginine 23a was carried out and the result supported the proposed intermediacy of β-arginine in the biosynthetic pathway to 1. Initial attempts to detect the putative arginine-2,3-aminomutase activity in cell-free extracts of S. griseochromogenes have not been successful so far. Feeding [2,3,4,6,6- ²H₅] -D- glucose resulted in blasticidin S 11 in which deuterium from H-2 and H-3 had been retained at H-6 and H-7, respectively. This interesting result led to the proposal of a novel mechanism for the introduction of a double bond in the hexeneuronic acid moiety of 1, and ruled out other mechanisms involving a β-eliminative dehydration process.
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