Streptolidine lactam

Cyanogen bromide ring closure of (417) was used to prepare streptolidine lactam (418), a guanidine-containing amino acid lactam moiety of the streptothricin antibiotic group (77BCJ2375), that moiety being a 4,5,6,7-tetrahydroimidazo[4,5-c]pyridine. 

In 1974, Goto and Ohgi prepared streptolidine 611 by a reaction of bromocyane with arabinose triamino-y-lactone followed by hydrolysis of intermediate 610 with hydrochloric acid (74TL1413). Kusumoto et al. at the same time reported the synthesis of streptolidine lactam 610, prepared in turn from 3,4-diamino-5-oxopiperi-done-2 609. Although the latter compound was not identified, its hydrolysis under reflux in 6 N hydrochloric acid led to the formation of streptolidine 611 (74TL1417). 

The streptolidine lactam (1), a component of the streptothricin group of antibiotics, has been synthesized as outlined in Scheme 1 o-Glucose has been used as an optically active source material for the synthesis of a-multistriatin (2), a beetle hormone, which is summarized in Scheme 2, and of (- )-c/j-rose oxide (3), shown in Scheme 3. ... 

Maruoka and coworkers described a direct phase-transfer-catalyzed Mannich reaction of the glycine imine ester 65a with a-imino ester. N-spiro quaternary ammonium bromide (S,S)-31c was identified as an efficient catalyst under LL (aqueous NaOH-mesitylene) phase-transfer conditions (Scheme 12.12) [114]. The usefulness of the Mannich adduct 86 was further demonstrated by the conversion into an optically pure precursor 87 of streptolidine lactam. 

Scheme 12.12 Asymmetric phase-transfer catalytic Mannich reaction of glycine imine ester 65a with a-amino ester and its further conversion into streptolidine lactam precursor 87.

Streptolidine (473), a guanidinoamino-acid that occurs as a component of the streptothricin group of antibiotics, has been synthesized by way of the lactam form (472) of (2S, 35,4i )-2,3,5-triamino-4-hydroxypentanoic acid (Scheme 154) 936 2R, 35, 45)-4-Amino-3-hydroxy-2-methyl-5-(pyrid-3-yl)pentanoic acid (474), a component of the antibiotic pyridomycin, has been derived from 3-deoxy-l,2 5,6-di-0-isopropylidene-3-C-methyl-a-D-allofuranose by the sequence of reactions outlined in Scheme 155. ... 

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