Studies on the biosynthesis of the streptolidine moiety of streptothricin F Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/rj430686h

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  • The loss of all deuterium labels from previous feedings of [2-²H]-, [3,3-²H₂]-, and [2,3,3-²H₃]arginines had indicated the possible intermediacy of β-hydroxy- and β-ketoarginine (30 and 31, respectively) in the biosynthesis of the streptolidine portion of streptothricin F (la). In order to confirm or refute this evidence, D,L-[2,3,3,5,5-²H₅]- arginine (32) was synthesized via a 4 step route from diethyl acetamidomalonate (90). The subsequent incorporation of 32 into la provided confirmation of the previous findings, thus further implicating the intermediacy of 31 and possibly one of the β-hydroxyarginine diastereomers. The erythro- and threo-β-hydroxy-L-[5,5-²H₂]arginines (131a and 131b, respectively) were then synthesized using a 1,3-dipolar cycloaddition strategy in which the reaction of in situ generated nitrone 116 with 2 (S)-vinylglycine derivative 117 afforded the diastereomeric isoxazolidines, 115. Feeding and trapping experiments using the labeled and unlabeled β-hydroxyarginines, respectively, indicated that these compounds were not intermediates in the biosynthesis of streptolidine. For the purpose of testing a second proposed pathway to streptolidine involving the rearrangement of 31 to the (3S, 4R)-epoxide 33, D, L-[3, 3, 4, 4 -² H₄]arginine (97) was synthesized from acetic acid-d₄. A feeding of this material generated la labeled at C-4 and at C-3 of the streptolidine portion, fully in agreement with such a proposal.
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