37248-47-8

Basic information

• Product Name: Validamycin
• Synonyms: valimon;VALIDACIN;VALIDAMYCIN;VALIDAMYCIN A;((4,5,6-trihydroxy-3-(hydroxymethyl)-2-cyclohexen-1-yl)amino)-,(1s-(1-alpha,4;(1s-(1a,4a,5b,6a))-1,5,6-trideoxy-3-o-b-d-glucopyranosyl-5-(hydroxymethyl)-1-(;(1s-(1alpha,4alpha,5beta,6alpha))-1,5,6-trideoxy-4-o-beta-d-glucopyrano;(4,5,6-trihydroxy-3-(hydroxymethyl)-=2-cyclohexen-1-yl)amino)-d-chiro-inositol
• CAS NO: 37248-47-8
• Molecular Formula: C₂₀H₃₅NO₁₃
• Molecular Weight: 497.49
• EINECS: 1806241-263-5
• Product Categories: FUNGICIDE;NULL
• Mol File: 37248-47-8.mol
• Article Data: 6

Chemical Properties

• Melting Point: 130-135°C
• Boiling Point: 813.7 °C at 760 mmHg
• Flash Point: 445.9 °C
• Appearance: white powder
• Density: 1.69 g/cm³
• Vapor Pressure: 0mmHg at 25°C
• Refractive Index: 1.689
• Storage Temp.: 0-6°C
• PKA: 6.0(at 25℃)
• Water Solubility: Readily soluble
• CAS DataBase Reference: Validamycin(CAS DataBase Reference)
• NIST Chemistry Reference: Validamycin(37248-47-8)
• EPA Substance Registry System: Validamycin(37248-47-8)

Safety Data

• Hazardous Substances Data: 37248-47-8(Hazardous Substances Data)

Usage

Description

Validamycin A is produced by the fermentation of Streptomyces hygroscopicus var. limoneus nov. var (30). Structure revised (31). Colorless, odorless, hygroscopic powder. V.p. Negligible at room temperature. Solubility: Readily soluble in water, soluble in methanol, dimethylformamide and dimethyl sulfoxide. Slightly soluble in ethanol and acetone. Sparingly soluble in diethyl ether and ethyl acetate. pKa 6.0 Stability [α]24D + 110? (water).

Uses

Different sources of media describe the Uses of 37248-47-8 differently. You can refer to the following data:
1. Validamycin A (>70%) Hydrochloride Salt is a metabolite of Validamycin A (>70%) (V943430) which is an antibiotic fungicide that inhibits trehalase activity in plants, insects, and fungi.
2. Validamycin A is the major analogue of a family of cyclitol disaccharides isolated from Streptomyces hygroscopicus var. limoneus by researchers at Takeda in 1970. Although commonly regarded as an aminoglycoside, validamycin shares little in common with conventional aminoglycosides such as streptomycin and gentamicin. Validamycin A is a potent antifungal agent and is used to control fungi in crop production. Validamycin A acts as a potent inhibitor of trehalase, an important enzyme in carbohydrate storage and ultilisation in fungi.
3. Validamycin A is used for the control of Rhizoctonia diseases in rice (sheath blight), potatoes, vegetables, strawberries, tobacco and other crops.

Definition

ChEBI: A member of the class of validamycins that is (1R,2S,3S,4S,6R)-4-amino-6-(hydroxymethyl)cyclohexane-1,2,3-triol in which the hydroxy group at position 1 has been converted to its beta-D-glucoside and in which one of the hydrogens attached to the nitrogen is replaced by a (1R,4R,5R,6S)-4,5,6-trihydroxy-3-(hydroxymethyl)cycloh x-2-en-1-yl group. It is the major validamycin produced by Streptomyces hygroscopicus.

Pharmacology

Validamycin A specifically inhibits trehalase in R. solani AG-1 in a competitive manner between validoxylamine A (the possible active form of validamycin A) and the substrate, trehalose (33). Because trehalose is a storage carbohydrate in some fungi, trehalase is suggested to play an essential role for the digestion of trehalose to D-glucose and for its transportation to the hyphal tips (34).

Metabolic pathway

Validamycin A is an effective fungistatic (as opposed to fungicidal) antibiotic which has a very low toxicity to mammals and fish. This is presumably a consequence of its selective mode of action, the inhibition of trehalase. It is readily degraded under environmental conditions.

Degradation

Validamycin A is stable at room temperature in neutral or alkaline media but is unstable in acidic media.

Toxicity evaluation

Acute oral LD50 for rats and mice >20 g/kg. Acute percutaneous LD50 for rats >5 g/kg. Nonirritating to skin (rabbits). Not a skin sensitiser (guinea pigs). Inhalation LC50 (4 h) for rats >5 mg/L air. NOEL: In 90-d feeding trials, rats receiving 1 g/kg of diet and mice receiving 2 g/kg of diet showed no ill-effects. In 2-y feeding trials, NOEL for rats was 40.4 mg/kg daily. Toxicity Class WHO (a.i.) III; EPA (formulation) IV.

InChI:InChI=1/C20H35NO13/c22-3-6-1-8(12(26)15(29)11(6)25)21-9-2-7(4-23)19(17(31)13(9)27)34-20-18(32)16(30)14(28)10(5-24)33-20/h1,7-32H,2-5H2

Synthetic route

7,2'',3'',4'',6''-penta-O-acetyl-2,3,4',5',6',7'-hexa-O-benzylvalidamycin A (86733-63-3) → validamycin A (37248-47-8)

Conditions	Yield
With ammonia; sodium In tetrahydrofuran at -78℃; for 6h;
With ammonium chloride; sodium 1) liq NH3, THF, -70 deg C, 4 h 20 min, 2) room temp., 4.5 h; Multistep reaction;

validamycin A undeca-O-acetate (86733-64-4, 121468-80-2) → validamycin A (37248-47-8)

Conditions	Yield
With sodium methylate In methanol for 5h; Ambient temperature;

validamycin A undecabenzyl ether (73482-11-8) → validamycin A (37248-47-8)

Conditions	Yield
With ammonium chloride; sodium 1) liq NH3, THF, -70 deg C, 4 h 20 min, 2) room temp., 4.5 h; Multistep reaction;

D-Glucose (2280-44-6) + culture medium → validamine (32780-32-8) + valienamine (38231-86-6) + validoxylamine A (39318-73-5, 81691-72-7, 81739-22-2) + validamycin A (37248-47-8)

Conditions	Yield
With Streptomyces hygroscopicus var. limoneus In water at 28℃; for 168h; Further byproducts.;

D-Glucose (2280-44-6) + culture medium → validamine (32780-32-8) + valienamine (38231-86-6) + validamycin A (37248-47-8) + validamycin B

Conditions	Yield
With Streptomyces hygroscopicus var. limoneus In water at 28℃; for 168h; Further byproducts.;

2,3,4',5',6',7'-hexa-O-benzylvalidoxylamine A (86733-61-1) → validamycin A (37248-47-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: 55.7 percent / imidazole / CHCl3 / 40 h / Heating 2: 74.2 percent / silver trifluoromethanesulphonate, 1,1,3,3-tetramethylurea / CH2Cl2 / 4.5 h / Ambient temperature 3: 1) sodium, 2) ammonium chloride / 1) liq NH3, THF, -70 deg C, 4 h 20 min, 2) room temp., 4.5 h View Scheme
Multi-step reaction with 3 steps 1: 61 percent / imidazole / CHCl3 / 48 h / Heating 2: 84 percent / silver trifluoromethanesulphonate, 1,1,3,3-tetramethylurea / CH2Cl2 / 10 h / Ambient temperature 3: liquid ammonia, sodium / tetrahydrofuran / 6 h / -78 °C View Scheme

7-O-acetyl-2,3,4',5',6',7'-hexa-O-benzylvalidoxylamine A (86733-62-2) → validamycin A (37248-47-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 74.2 percent / silver trifluoromethanesulphonate, 1,1,3,3-tetramethylurea / CH2Cl2 / 4.5 h / Ambient temperature 2: 1) sodium, 2) ammonium chloride / 1) liq NH3, THF, -70 deg C, 4 h 20 min, 2) room temp., 4.5 h View Scheme
Multi-step reaction with 2 steps 1: 84 percent / silver trifluoromethanesulphonate, 1,1,3,3-tetramethylurea / CH2Cl2 / 10 h / Ambient temperature 2: liquid ammonia, sodium / tetrahydrofuran / 6 h / -78 °C View Scheme

2,3,4',5',6',7'-hexa-O-benzyl-4,7-O-benzylidenevalidoxylamine A (86756-42-5, 102131-10-2) → validamycin A (37248-47-8)

Conditions	Yield
Multi-step reaction with 4 steps 1: 59 percent / aq acetic acid (80percent) / 20 h / 60 °C 2: 55.7 percent / imidazole / CHCl3 / 40 h / Heating 3: 74.2 percent / silver trifluoromethanesulphonate, 1,1,3,3-tetramethylurea / CH2Cl2 / 4.5 h / Ambient temperature 4: 1) sodium, 2) ammonium chloride / 1) liq NH3, THF, -70 deg C, 4 h 20 min, 2) room temp., 4.5 h View Scheme
Multi-step reaction with 4 steps 1: 86 percent / aq. 80percent acetic acid / 9 h / 50 °C 2: 61 percent / imidazole / CHCl3 / 48 h / Heating 3: 84 percent / silver trifluoromethanesulphonate, 1,1,3,3-tetramethylurea / CH2Cl2 / 10 h / Ambient temperature 4: liquid ammonia, sodium / tetrahydrofuran / 6 h / -78 °C View Scheme

4,7-O-benzylidenevalidoxylamine A hexa-O-acetate (86733-60-0, 102131-09-9) → validamycin A (37248-47-8)

Conditions

Yield

Multi-step reaction with 5 steps 1: 1)methanolic sodium methoxyde (1M), 2) sodium hydride / 1) methanol, room temp., 50 min, 2) DMF, room temp., 23 h 2: 59 percent / aq acetic acid (80percent) / 20 h / 60 °C 3: 55.7 percent / imidazole / CHCl3 / 40 h / Heating 4: 74.2 percent / silver trifluoromethanesulphonate, 1,1,3,3-tetramethylurea / CH2Cl2 / 4.5 h / Ambient temperature 5: 1) sodium, 2) ammonium chloride / 1) liq NH3, THF, -70 deg C, 4 h 20 min, 2) room temp., 4.5 h View Scheme

1D-(1,3,6/2)-6-amino-4-benzyloxymethyl-1,2,3-tri-O-benzyltrihydroxycyclohex-4-ene (114779-32-7) → validamycin A (37248-47-8)

Conditions

Yield

Multi-step reaction with 8 steps 1: 75 percent / propan-2-ol / 110 h / 120 °C 2: 89 percent / sodium hydride, di-imidazolyl sulphone / dimethylformamide / 1.5 h / 50 °C 3: 91 percent / propan-2-ol / 4 h / 80 °C 4: 75 percent / H2 / Ranei nickel T-4 / dioxane; ethanol / 6 h / 60 °C 5: 86 percent / aq. 80percent acetic acid / 9 h / 50 °C 6: 61 percent / imidazole / CHCl3 / 48 h / Heating 7: 84 percent / silver trifluoromethanesulphonate, 1,1,3,3-tetramethylurea / CH2Cl2 / 10 h / Ambient temperature 8: liquid ammonia, sodium / tetrahydrofuran / 6 h / -78 °C View Scheme

(1aR,2S,3S,3aR,5R,7aS,7bR)-2,3-Bis-benzyloxy-5-phenyl-hexahydro-1,4,6-trioxa-cyclopropa[a]naphthalene (114779-35-0, 148347-66-4) → validamycin A (37248-47-8)

Conditions

Yield

Multi-step reaction with 8 steps 1: 75 percent / propan-2-ol / 110 h / 120 °C 2: 89 percent / sodium hydride, di-imidazolyl sulphone / dimethylformamide / 1.5 h / 50 °C 3: 91 percent / propan-2-ol / 4 h / 80 °C 4: 75 percent / H2 / Ranei nickel T-4 / dioxane; ethanol / 6 h / 60 °C 5: 86 percent / aq. 80percent acetic acid / 9 h / 50 °C 6: 61 percent / imidazole / CHCl3 / 48 h / Heating 7: 84 percent / silver trifluoromethanesulphonate, 1,1,3,3-tetramethylurea / CH2Cl2 / 10 h / Ambient temperature 8: liquid ammonia, sodium / tetrahydrofuran / 6 h / -78 °C View Scheme

(1S,2R,5R,7R,8S,10S)-8,9-dibenzyloxy-11-<(1S)-(1,4,6/5)-4,5,6-tribenzyloxy-3-benzyloxymethylcyclohex-2enyl>-5-phenyl-4,6-dioxa-11-azatricyclo<8.1.0.0.2,7>undecane (117295-71-3) → validamycin A (37248-47-8)

Conditions

Yield

Multi-step reaction with 6 steps 1: 91 percent / propan-2-ol / 4 h / 80 °C 2: 75 percent / H2 / Ranei nickel T-4 / dioxane; ethanol / 6 h / 60 °C 3: 86 percent / aq. 80percent acetic acid / 9 h / 50 °C 4: 61 percent / imidazole / CHCl3 / 48 h / Heating 5: 84 percent / silver trifluoromethanesulphonate, 1,1,3,3-tetramethylurea / CH2Cl2 / 10 h / Ambient temperature 6: liquid ammonia, sodium / tetrahydrofuran / 6 h / -78 °C View Scheme

2,3,4',5',6',7'-hexa-O-benzyl-4,5-O-benzyllidenevalidoxylamine B (117320-21-5) → validamycin A (37248-47-8)

Conditions

Yield

Multi-step reaction with 7 steps 1: 89 percent / sodium hydride, di-imidazolyl sulphone / dimethylformamide / 1.5 h / 50 °C 2: 91 percent / propan-2-ol / 4 h / 80 °C 3: 75 percent / H2 / Ranei nickel T-4 / dioxane; ethanol / 6 h / 60 °C 4: 86 percent / aq. 80percent acetic acid / 9 h / 50 °C 5: 61 percent / imidazole / CHCl3 / 48 h / Heating 6: 84 percent / silver trifluoromethanesulphonate, 1,1,3,3-tetramethylurea / CH2Cl2 / 10 h / Ambient temperature 7: liquid ammonia, sodium / tetrahydrofuran / 6 h / -78 °C View Scheme

2,3,4',5',6',7'-hexa-O-benzyl-4,7-O-benzylidene-6-p-toluenesulphenylvalidoxylamine A (117295-72-4) → validamycin A (37248-47-8)

Conditions	Yield
Multi-step reaction with 5 steps 1: 75 percent / H2 / Ranei nickel T-4 / dioxane; ethanol / 6 h / 60 °C 2: 86 percent / aq. 80percent acetic acid / 9 h / 50 °C 3: 61 percent / imidazole / CHCl3 / 48 h / Heating 4: 84 percent / silver trifluoromethanesulphonate, 1,1,3,3-tetramethylurea / CH2Cl2 / 10 h / Ambient temperature 5: liquid ammonia, sodium / tetrahydrofuran / 6 h / -78 °C View Scheme

uridine 5′-diphosphate glucose disodium salt + (+)-validoxylamine A (38665-10-0) → validamycin A (37248-47-8)

Conditions	Yield
With recombinant His6-tagged validamycin glycosyltransferase at 30℃; pH=7.5; aq. buffer; Enzymatic reaction;

acetic anhydride (108-24-7) + validamycin A (37248-47-8) → validamycin A undeca-O-acetate (86733-64-4, 121468-80-2)

Conditions	Yield
In pyridine Ambient temperature;	60%
Yield given;

validamycin A (37248-47-8) → 1L-(1,2,4/3)-1-Methyl-2,3,4-cyclohexantriol (92621-62-0)

Conditions	Yield
(reduction);

validamycin A (37248-47-8) → 5a-carba-1,5-anhydro-L-iditol (139561-46-9)

Conditions	Yield
(reduction);

benzyl bromide (100-39-0) + validamycin A (37248-47-8) → validamycin A undecabenzyl ether (73482-11-8)

Conditions	Yield
With sodium hydride 1) DMF, r.t., 1 h, 2) r.t., 23 h; Yield given. Multistep reaction;

2-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrile (58632-95-4) + acetic anhydride (108-24-7) + validamycin A (37248-47-8) → N-(tert-butyloxycarbonyl)-4,5,6-tri-O-acetyl-valienamine-3-aldehyde (223608-50-2) + Acetic acid (1S,2S,3R,4S,6S)-2,3-diacetoxy-6-tert-butoxycarbonylamino-4-formyl-cyclohexyl ester

Conditions	Yield
Multistep reaction;	A 8 mg B n/a

2-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrile (58632-95-4) + acetic anhydride (108-24-7) + validamycin A (37248-47-8) → N-(tert-butyloxycarbonyl)-4,5,6-tri-O-acetyl-valienamine + N-(tert-butyloxycarbonyl)-4,5,6-tri-O-acetyl-validamine

Conditions	Yield
Multistep reaction. Title compound not separated from byproducts;

2-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrile (58632-95-4) + acetic anhydride (108-24-7) + validamycin A (37248-47-8) + mono-4-methoxytrityl chloride (14470-28-1) → N-(tert-butoxycarbonyl)-4,5,6-tri-O-acetyl-7-(4-monomethoxytrityl)-valienamine + N-(tert-butoxycarbonyl)-4,5,6-tri-O-acetyl-7-(4-monomethoxytrityl)-validamine

Conditions	Yield
Multistep reaction. Title compound not separated from byproducts;

validamycin A (37248-47-8) → (+)-validoxylamine A (38665-10-0) + validamine (32780-32-8) + valienamine (38231-86-6)

Conditions	Yield
With ammonium sulfate; Flavobacterium saccharophilum IFO 13984; magnesium sulfate In phosphate buffer for 96h; pH=7.1; Hydrolysis; Title compound not separated from byproducts;

2-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrile (58632-95-4) + validamycin A (37248-47-8) + N-(tert-butyloxycarbonyl)-valienamide (85240-37-5) → N-(tert-butyloxycarbonyl)-7-(4-monomethoxytrityl)-valienamine + N-(tert-butyloxycarbonyl)-7-(4-monomethoxytrityl)-validamine

Conditions

Yield

Stage #1: validamycin A With ammonium sulfate; Flavobacterium saccharophilum IFO 13984; magnesium sulfate In phosphate buffer for 96h; pH=7.1; Hydrolysis; Stage #2: 2-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrile In 1,4-dioxane; water at 20℃; Acylation; Stage #3: N-(tert-butyloxycarbonyl)-valienamide With dmap; triethylamine In dichloromethane at 20℃; for 168000h; Etherification; Title compound not separated from byproducts;

2-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrile (58632-95-4) + validamycin A (37248-47-8) → N-(tert-butyloxycarbonyl)-valienamide (85240-37-5) + N-(tert-butyloxycarbonyl)-validamine

Conditions	Yield
Stage #1: validamycin A With ammonium sulfate; Flavobacterium saccharophilum IFO 13984; magnesium sulfate In phosphate buffer for 96h; pH=7.1; Hydrolysis; Stage #2: 2-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrile In 1,4-dioxane; water at 20℃; Acylation; Title compound not separated from byproducts;

validamycin A (37248-47-8) → (+)-validoxylamine A (38665-10-0)

Conditions	Yield
With acid
With sulfuric acid; acetic acid Inert atmosphere;

validamycin A (37248-47-8) → C21H29NO8 (1316288-57-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: sulfuric acid; acetic acid / Inert atmosphere 2: toluene-4-sulfonic acid / N,N-dimethyl-formamide / 3 h / 60 °C / Inert atmosphere View Scheme

validamycin A (37248-47-8) → 1D-(1,3,6/2)-6-amino-4-benzyloxymethyl-1,2,3-tri-O-benzyltrihydroxycyclohex-4-ene (114779-32-7) + 2,3,4,7-tetra-O-benzylvalidamine (139499-19-7) + (2R,3S,4R,5R)-2,3,4-tris(benzyloxy)-5-[(benzyloxy)methyl]cyclohexanone (124330-57-0) + (4R,5S,6R)-4,5,6-tris(benzyloxy)-3-((benzyloxy)methyl)-2-cyclohexen-1-one (110391-10-1)

Conditions	Yield
Multi-step reaction with 3 steps 1: sulfuric acid; acetic acid / Inert atmosphere 2: sodium hydride / N,N-dimethyl-formamide / Inert atmosphere 3: N-Bromosuccinimide / water; acetonitrile / 15 h / 20 °C / Inert atmosphere View Scheme

validamycin A (37248-47-8) → ((1R,2R,3S,4S,5S)-2,3,4-tris(benzyloxy)-5-(((1S,4R,5S,6S)-4,5,6-tris(benzyloxy)-3-((benzyloxy)methyl)cyclohex-2-en-1-yl)amino)cyclohexyl)methanol (137063-37-7)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: sulfuric acid; acetic acid / Inert atmosphere 2.1: toluene-4-sulfonic acid / N,N-dimethyl-formamide / 3 h / 60 °C / Inert atmosphere 3.1: sodium hydride / N,N-dimethyl-formamide / 0.5 h / 0 °C / Inert atmosphere 3.2: 3 h / 20 °C / Inert atmosphere 4.1: diisobutylaluminium hydride / hexane; dichloromethane / 6.5 h / 0 - 20 °C / Inert atmosphere View Scheme

validamycin A (37248-47-8) → (4aR,6S,7S,8S,8aR)-7,8-bis(benzyloxy)-2-phenyl-N-((1S,4R,5S,6S)-4,5,6-tris(benzyloxy)-3-((benzyloxy)methyl)cyclohex-2-en-1-yl)hexahydro-4H-benzo[d][1,3]dioxin-6-amine (86756-42-5, 102131-10-2)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: sulfuric acid; acetic acid / Inert atmosphere 2.1: toluene-4-sulfonic acid / N,N-dimethyl-formamide / 3 h / 60 °C / Inert atmosphere 3.1: sodium hydride / N,N-dimethyl-formamide / 0.5 h / 0 °C / Inert atmosphere 3.2: 3 h / 20 °C / Inert atmosphere View Scheme

Upstream product

• 73482-11-8 validamycin A undecabenzyl ether 
• 2280-44-6 D-Glucose 
• 38665-10-0 (+)-validoxylamine A 
• 86964-83-2 C₅₁H₆₁NO₂₂ 
• 86975-62-4 Benzoic acid (3aS,4R,5R,7S,7aS)-7-amino-2,2-dimethyl-4-((2R,3R,4S,5R,6R)-3,4,5-triacetoxy-6-acetoxymethyl-tetrahydro-pyran-2-yloxy)-hexahydro-benzo[1,3]dioxol-5-ylmethyl ester 
• 74766-86-2 DL-3,4-di-O-Acetyl-1,2-anhydro-(1,2,3/4)-5-benzoyloxymethyl-5-cyclohexene-1,2,3,4-tetrol 
• 86964-84-3 C₅₂H₆₁NO₂₄ 
• 117295-72-4 2,3,4',5',6',7'-hexa-O-benzyl-4,7-O-benzylidene-6-p-toluenesulphenylvalidoxylamine A 
• 117320-21-5 2,3,4',5',6',7'-hexa-O-benzyl-4,5-O-benzyllidenevalidoxylamine B 
• 117295-71-3 (1S,2R,5R,7R,8S,10S)-8,9-dibenzyloxy-11-<(1S)-(1,4,6/5)-4,5,6-tribenzyloxy-3-benzyloxymethylcyclohex-2enyl>-5-phenyl-4,6-dioxa-11-azatricyclo<8.1.0.0.^2,7>undecane 
• 114779-35-0 (1aR,2S,3S,3aR,5R,7aS,7bR)-2,3-Bis-benzyloxy-5-phenyl-hexahydro-1,4,6-trioxa-cyclopropa[a]naphthalene 
• 114779-32-7 1D-(1,3,6/2)-6-amino-4-benzyloxymethyl-1,2,3-tri-O-benzyltrihydroxycyclohex-4-ene 
• 86733-60-0 4,7-O-benzylidenevalidoxylamine A hexa-O-acetate 
• 86756-42-5 2,3,4',5',6',7'-hexa-O-benzyl-4,7-O-benzylidenevalidoxylamine A 

Downstream Products

• 92621-62-0 1L-(1,2,4/3)-1-Methyl-2,3,4-cyclohexantriol 
• 139561-46-9 5a-carba-1,5-anhydro-L-iditol 
• 223608-50-2 N-(tert-butyloxycarbonyl)-4,5,6-tri-O-acetyl-valienamine-3-aldehyde 
• 38665-10-0 (+)-validoxylamine A 
• 32780-32-8 validamine 
• 38231-86-6 valienamine 
• 102583-47-1 validamycin B 
• 124330-54-7 (1S,4R,5S,6S)-4,5,6-tris(benzyloxy)-3-((benzyloxy)methyl)-N-((1S,2S,3S,4R,5R)-2,3,4-tris(benzyloxy)-5-((benzyloxy)methyl)cyclohexyl)cyclohex-2-enamine 
• 86756-42-5 (4aR,6S,7S,8S,8aR)-7,8-bis(benzyloxy)-2-phenyl-N-((1S,4R,5S,6S)-4,5,6-tris(benzyloxy)-3-((benzyloxy)methyl)cyclohex-2-en-1-yl)hexahydro-4H-benzo[d][1,3]dioxin-6-amine 
• 137063-37-7 ((1R,2R,3S,4S,5S)-2,3,4-tris(benzyloxy)-5-(((1S,4R,5S,6S)-4,5,6-tris(benzyloxy)-3-((benzyloxy)methyl)cyclohex-2-en-1-yl)amino)cyclohexyl)methanol 
• 114779-32-7 1D-(1,3,6/2)-6-amino-4-benzyloxymethyl-1,2,3-tri-O-benzyltrihydroxycyclohex-4-ene 
• 139499-19-7 2,3,4,7-tetra-O-benzylvalidamine 
• 124330-57-0 (2R,3S,4R,5R)-2,3,4-tris(benzyloxy)-5-[(benzyloxy)methyl]cyclohexanone 
• 110391-10-1 (4R,5S,6R)-4,5,6-tris(benzyloxy)-3-((benzyloxy)methyl)-2-cyclohexen-1-one 

Relevant articles and documents

Catalytic analysis of the validamycin glycosyltransferase (ValG) and enzymatic production of 4″-epi-validamycin A

ValG is a glycosyltransferase (GT) that is responsible for the glucosylation of validoxylamine A to validamycin A. To explore the potential utilization of ValG as a tool for the production of validamycin analogues, a number of nucleotidyldiphosphate-sugars were evaluated as alternative substrates for VaIG. The results indicated that in addition to its natural substrate, UDP-glucose, ValG also efficiently utilized UDP-galactose as sugar donor and resulted in the production of an unnatural compound, 4″-epi-validamycin A. The new compound demonstrated a moderate growth inhibitory activity against the plant fungal pathogen Rhizoctonia solani (=Pellicularia sasakii). A comparative analysis of ValG with its homologous proteins revealed that ValG contains an unusual DTG motif, in place of the DXD motif proposed for metal ion binding and/or NDP-sugar binding and commonly found in other glycosyltransferases. Site-directed mutagenesis of the DTG motif of ValG to DCD altered its preferences for metal ion binding, but did not seem to affect its substrate specificity.

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.

A TOTAL SYNTHESIS OF 6"-EPIVALIDAMYCIN A AND ITS DIASTEREOMER

A total synthesis of the 6"-epimer of validamycin A and its diastereomer has been accomplished by a coupling reaction of the racemic peracyl 5,6-dihydroxy-1-hydroxymethyl-1,3-cyclohexadiene monoepoxide, the precursor of the unsaturated branched-chain cyclitol portion, with the protected β-D-glucopyranosylvalidamine, followed by acid hydrolysis and O-deacylation.