79527-24-5

Upstream product

• 1125-88-8 benzaldehyde dimethyl acetal 
• 38665-10-0 (+)-validoxylamine A 
• 108-24-7 acetic anhydride 
• 82252-27-5 N-<(1SR)-5,6-di-O-acetyl-4,7O-benzylidene-(1,4,6/5)-4,5,6-trihydroxy-3-(hydroxymethyl)-2-cyclohexenyl>-(1SR)-2,3:4,7-di-O-isopropylidenevalidamine 
• 82252-27-5 Acetic acid (6R,7R,8R,8aS)-8-acetoxy-2-phenyl-6-((3aR,4S,5aS,9aS,9bR)-2,2,8,8-tetramethyl-hexahydro-[1,3]dioxolo[4',5':3,4]benzo[1,2-d][1,3]dioxin-4-ylamino)-6,7,8,8a-tetrahydro-4H-benzo[1,3]dioxin-7-yl ester 
• 79527-23-4 Acetic acid (1S,2R,5R,6S)-5,6-diacetoxy-4-acetoxymethyl-2-((3aR,4R,5aS,9aS,9bR)-2,2,8,8-tetramethyl-hexahydro-[1,3]dioxolo[4',5':3,4]benzo[1,2-d][1,3]dioxin-4-ylamino)-cyclohex-3-enyl ester 
• 82252-27-5 Acetic acid (6S,7S,8S,8aR)-8-acetoxy-2-phenyl-6-((3aR,4R,5aS,9aS,9bR)-2,2,8,8-tetramethyl-hexahydro-[1,3]dioxolo[4',5':3,4]benzo[1,2-d][1,3]dioxin-4-ylamino)-6,7,8,8a-tetrahydro-4H-benzo[1,3]dioxin-7-yl ester 
• 79527-14-3 D,L-1,7:2,3-di-O-isopropylidene-(1,3/2,4,6)-4-bromo-6-hydroxymethyl-1,2,3-cyclohexanetriol 
• 79527-15-4 DL-2,3:4,7-di-O-isopropylidene-(1,2,4/3,5)-2,3,4-trihydroxy-5-(hydroxymethyl)cyclohexylamine 
• 79527-13-2 DL-(1,3/2,4,6)-4-bromo-6-hydroxymethyl-1,2,3-cyclohexanetriol 
• 70878-41-0 DL-1,2,3-tri-O-acetyl-(1,3/2,4,6)-6-acetoxymethyl-4-bromo-1,2,3-cyclohexanetriol 

Downstream Products

• 38665-10-0 (1R,2R,3S,6R)-4-Hydroxymethyl-6-((1S,2S,3S,4R,5R)-2,3,4-trihydroxy-5-hydroxymethyl-cyclohexylamino)-cyclohex-4-ene-1,2,3-triol 
• 38665-10-0 DL-validoxylamine A 
• 124330-59-2 (4R,5R)-2,4-diacetoxy-5-acetoxymethylcyclohex-2-en-1-one 

Relevant academic research and scientific papers

Synthetic studies on antibiotic validamycins. Part 13. Total synthesis of (+)-validamycins A and E, and related compounds

(+)-Validoxylamine A (1) has been completely synthesized by deoxygenation of the validoxylamine B derivative (6) through formation of the aziridine, nucleophilic displacement with toluenethiol, reduction with Raney nickel, and deprotection. The validoxylamine A derivative (10) obtained was convertible, by glycosylation followed by deprotection, into validamycins A (2), E (3), and their analogues, which constitutes a total synthesis thereof.

Synthetic Studies on Antibiotic Validamycins. Part 11. Synthesis of Validamycin A

The antibiotic validamycin A (1a) has been synthesized for the first time (as its undeca-O-acetate) by glycosylation of the partially protected derivative (8) of the aglycone, validoxylamine A (2a), with 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl chloride (11), followed by deprotection, thereby establishing the structure previously assigned.The totally O-acetylated derivative (19) of 7-deoxyvalidamycin A has been synthesized in a similar fashion.

Synthetic Studies on the Validamycines. 10. Total Synthesis of DL-Validoxylamines A and B.

The first synthesis of racemic validoxylamine A (3) and B (4), constituents of antibiotic validamycins, is described.For construction of these types of pseudodisaccharides containing an imino linkage, a coupling reaction of the protected anhydro derivative of DL-pentahydroxy(hydroxymethyl)cyclohexane (5) with the DL-trihydroxy(hydroxymethyl)cyclohexylamine or -cyclohexenylamine (6 or 7) was untertaken.All possible diastereoisomers (four pairs of enantiomeres) formed by the reaction of 5 with 6, employed for synthesis of 4, could be separated by chromatography on silica gel, and the relative configuration in two of the enantiomeric pairs, deduced on the basis of 1H-NMR spectroscopy, were confirmed by identification of one pair with an authentic chiral sample 4.On the other hand, the intermediate enantiomeric pair 13a obtained by a coupling of the appropriate epoxide 5 and amine 7 underwent mainly dehydration with sulfuryl chloride in pyridine to give the pair of enantiomers 19a, one of which was the protected derivative of 3.In contrast, the diastereomeric pair of enantiomers 13b yielded selectively the chloride 18b, which was then transformed into the enantiomeric pair 21b by dehydrochlorination followed by deprotection.

SYNTHESIS OF DL-VALIDOXYLAMINE A

The first total synthesis of DL-validoxylamine A, one of the components of the antibiotic validamycin complex, is described.

SYNTHESIS OF SOME RACEMIC ISOMERS OF VALIDOXYLAMINE A

Two racemic isomers of validoxylamine A were synthesized by the condensation reaction of the blocked DL-validamine and the allyl bromide, the precursor of the unsaturated branched-chain cyclitol moiety.