85240-37-5

Upstream product

• 41840-28-2 S-tert-butoxycarbonyl-4,6-dimethyl-2-mercaptopyrimidine 
• 38231-86-6 valienamine 
• 58632-95-4 2-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrile 
• 37248-47-8 validamycin A 

Downstream Products

• 913069-83-7 Succinic acid mono-((3S,4S,5S,6R)-3-tert-butoxycarbonylamino-4,5,6-trihydroxy-cyclohex-1-enylmethyl) ester 
• 85281-06-7 <1S-(endo,exo,endo)>-6,7,8-trihydroxy-1-(hydroxymethyl)-3-oxo-2-oxa-4-azabicyclo<3.3.1>nonane 
• 83465-22-9 (1S,2S,3R,4S,5S)-1-amino-5-hydroxymethyl-2,3,4,5-tetrahydroxycyclohexane 
• 913069-86-0 Succinic acid mono-[(3S,4S,5S,6R)-3-(9H-fluoren-9-ylmethoxycarbonylamino)-4,5,6-trihydroxy-cyclohex-1-enylmethyl] ester 
• 913069-85-9 N-Fmoc-valienamine 

Relevant academic research and scientific papers

STEREOSELECTIVE CONVERSION OF VALIENAMINE AND VALIDAMINE INTO VALIOLAMINE

Methods are described for the stereoselective conversion of valienamine (2) and validamine (3) into valiolamine (1a), a new pseudo-amino sugar isolated from the fermentation broth of Streptomyces hygroscopicus subsp. limoneus and which is a stronger α-D-glucosidase inhibitor than 2 and 3.Treatment of the acyclic carbamates (4) of 2 with halogenation reagents led to ring closure to afford the halo cyclic carbamates (6), which were reductively dehalogenated and then hydrolyzed to give 1a.Similar treatment of the exomethylene acyclic carbamate (12), derived from 3 via 8-11, resulted in the formation of halo cyclic carbamates (14a,b), which were converted into 1a.The synthesis of epivaliolamine (1b), the C-1 epimer of 1a, starting from 2 and 3, is also described.

Synthesis of [7-3H]valienamine, [7-3H]valienone, [7-3H]valiolamine and [7-3H]valiolone from validamycin A

To investigate the biosynthetic pathway to the cyclitol moieties of acarbose and validamycin A, [7-3H]valienamine, [7-3H]valienone, [7-3H]valiolamine and [7-3H]valiolone were synthesized as plausible precursors. Valienamine together with validamine was isolated from the degradation of validamycin A by Flavobacterium saccharophilum and served as starting material for the synthesis. Validamine was removed partially at the stage of tritylation and completely after the oxidation of the primary hydroxy group at C-7 to the aldehyde. The resulting valienamine aldehyde was reduced with tritiated sodium borohydride to produce [7-3H]valienamine. The latter was converted to [7-3H]valiolamine by a synthetic route described in the literature. The 3H-labeled amines were oxidized to [7-3H]valienone and [7-3H]valiolone, respectively, using 3,5-di-tert-butyl-1,2-bezoquinone (DBQ) followed by hydrolysis with oxalic acid.