2595-05-3

Usage

Synthesis

Anhydrous DMSO (650 mL) was cooled to 18?20 °C under nitrogen in a 3-L roundbottomed glass flflask. DMSO solidififies at 18 °C and therefore it is important to keep the reaction mixture just above freezing point. To this cold solution was added P2O5 (142 g, 1.0 mol, 1 equivalent) in 3 portions under a N2 atmosphere. The addition of P2O5?to DMSO is exothermic, and if the mass temperature exceeds 28 °C, the color darkens and the product will be of inferior quality. The mixture was cooled to 18?20 °C between each addition. After addition of P2O5 was completed, the mixture was stirred at 18?25 °C for 10?15 min. 1,2:5,6-Di-O-isopropylidene-D-glucofuranose (260 g, 1.0 mol) was dissolved in anhydrous DMSO (1.3 L) and added over 30 min (maintaining the temperature at 18?25 °C) to the stirred solution of P2O5 in DMSO under a N2 atmosphere. The resulting solution was heated to 50?55 °C for 3 h. TLC (eluent: CH2Cl2:MeOH, 95:5) shows complete conversion of glucofuranose (Rf = 0.68) to ulose (Rf = 0.81). The reaction mixture was allowed to reach 25?30 °C and was extracted twice with methyl tert-butyl ether (MTBE 1.5 and 1 L) in a 6-L separation funnel. The combined MTBE layer (~4 L) was concentrated in vacuo (water-bath temperature set to 40 °C) to approximately 2 L and allowed to reach 25?30 °C. NaBH4 (24 g, 0.63 mol) was dissolved in water (1 L, 55.6 mol) at 0?10 °C, and the concentrated MTBE layer was added to the aqueous layer over 30 min to keep ?the temperature at 0?10 °C. TLC (eluent: EtOAc/heptane, 6:4) after 30 min shows ?full conversion of ulose (Rf = 0.53) to 1,2:5,6-di-O-isopropylidene-D-allofuranose (Rf = 0.39). The reaction mixture was allowed to reach 25?30 °C. CH2Cl2 (1 L) and water (500 mL) were added, and the layers were separated. The aqueous layer was extracted once more with CH2Cl2 (500 mL). The combined organic layers were concentrated in vacuo to an oil which was subsequently dissolved in MTBE (300 mL) and extracted with water (3 × 500 mL). The combined aqueous layers were extracted with CH2Cl2 (3 × 500 mL). The combined CH2Cl2 layers were dried (Na2SO4, 100 g), fifiltered, and concentrated in vacuo to provide the crude oil. Crystallization from cyclohexane (500 mL), washing of crystals with cold n-pentane, and drying hereof in vacuo afforded analytically pure 1,2:5,6-di-O-isopropylidene-D-allofuranose (191 g, 73%). Reference: Christensen, S. M.; Hansen, H. F.; Koch, T. Org. Proc. Res. Dev. 2004, 8, 777?780.

Chemical Properties

White Solid

Uses

Protected α-D-Allofuranose

InChI:InChI=1/C12H20O6/c1-11(2)14-5-6(16-11)8-7(13)9-10(15-8)18-12(3,4)17-9/h6-10,13H,5H2,1-4H3/t6-,7-,8-,9-,10-/m1/s1

Synthetic route

2,2,2-Trichloro-acetimidic acid (3aR,5R,6R,6aR)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yl ester → Diacetone D-glucose (2595-05-3)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In methanol for 2h; Ambient temperature;	100%

1,2:5,6-di-O-isopropylidene-α-D-hexofuran-3-ulose (2847-00-9) → Diacetone D-glucose (2595-05-3)

Conditions	Yield
With sodium tetrahydroborate In ethanol at 0 - 20℃; for 2h;	96%
With sodium tetrahydroborate In ethanol; water at 0℃; for 1h;	90%
With sodium tetrahydroborate In ethanol; water at 20℃; for 3h; stereoselective reaction;	84%

3-O-tetrahydropyranyl-1,2:5,6-di-O-isopropylidene-α-D-allofuranose (226943-46-0) → Diacetone D-glucose (2595-05-3)

Conditions	Yield
With water; O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate In acetonitrile at 75℃; for 0.5h;	91%
With iodine In methanol at 20℃; for 1h; acetal cleavage;	90%

3-O-(4,4'-dimethoxytrityl)-1,2:5,6-di-O-isopropylidene-α-D-allofuranose (226943-66-4) → Diacetone D-glucose (2595-05-3)

Conditions	Yield
With iodine In methanol at 20℃; for 1h; ether cleavage;	88%
With water; O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate In acetonitrile at 75℃; for 0.25h;	85%

1,2:5,6-di-O-isopropylidene-α-D-glucofuranose (582-52-5) → Diacetone D-glucose (2595-05-3)

Conditions	Yield
Stage #1: 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose With oxalyl dichloride; dimethyl sulfoxide; triethylamine In dichloromethane at -78℃; Stage #2: With sodium tetrahydroborate In methanol at 0℃;	85%
Stage #1: 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose With dipyridinium dichromate; acetic anhydride In dichloromethane Stage #2: With sodium tetrahydroborate In ethanol	83%
Stage #1: 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose With dimethyl sulfoxide; triethylamine; trifluoroacetic anhydride In dichloromethane at -65 - 20℃; Stage #2: With sodium tetrahydroborate In methanol at 0℃; for 1h;	82%

1,2:5,6-di-O-isopropylidene-α-D-hexofuran-3-ulose (2847-00-9) → Diacetone D-glucose (2595-05-3) + 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose (582-52-5)

Conditions	Yield
With sodium tetrahydroborate In methanol	A 4.49 g B n/a

1,2:5,6-di-O-isopropylidene-α-D-glucofuranose (582-52-5) + C6H6O2(OBn)3(OPiv)SP(S)(OEt)2 → Diacetone D-glucose (2595-05-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: CrO3; Ac2O; pyridine / CH2Cl2 / 1 h / 0 °C 2: 8.0 g / NaBH4 / ethanol / 0.5 h / 0 °C View Scheme
Multi-step reaction with 2 steps 1: CrO3; Ac2O; pyridine / CH2Cl2 / 2.5 h / 0 - 20 °C 2: 4.49 g / NaBH4 / methanol View Scheme
Multi-step reaction with 2 steps 1: 85 percent / PCC; 3 Angstroem molecular sieves; neutral alumina / CH2Cl2 / 15 h / 20 °C 2: 96 percent / NaBH4 / aq. ethanol / 2 h / 0 - 20 °C View Scheme

alpha-D-glucopyranose (492-62-6) → Diacetone D-glucose (2595-05-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: 32 percent / ZnCl2; H3PO4 / 30 h / 20 °C 2: 85 percent / PCC; 3 Angstroem molecular sieves; neutral alumina / CH2Cl2 / 15 h / 20 °C 3: 96 percent / NaBH4 / aq. ethanol / 2 h / 0 - 20 °C View Scheme

D-Glucose (2280-44-6) → Diacetone D-glucose (2595-05-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: 68 percent / ZnCl2; aq. H3PO4 / 36 h / 20 °C 2: 91 percent / pyridinium dichromate; acetic anhydride / CH2Cl2 / 4 h / 75 °C 3: 90 percent / NaBH4 / ethanol; H2O / 1 h / 0 °C View Scheme
Multi-step reaction with 3 steps 1: phosphoric acid; zinc(II) chloride / 36 h / Reflux 2: dipyridinium dichromate; acetic anhydride / dichloromethane / 2 h 3: sodium tetrahydroborate / ethanol / 2 h View Scheme
Multi-step reaction with 2 steps 1: zinc(II) chloride; phosphoric acid / acetone 2: acetic anhydride; pyridinium chlorochromate / dichloromethane View Scheme
Multi-step reaction with 3 steps 1: zinc(II) chloride; phosphoric acid 2: acetic anhydride; dipyridinium dichromate / dichloromethane 3: sodium tetrahydroborate / ethanol View Scheme
Multi-step reaction with 3 steps 1: sulfuric acid 2: chromium(VI) oxide; pyridine; acetic anhydride / dichloromethane / 0.42 h / Cooling with ice 3: sodium tetrahydroborate; ethanol / Cooling with ice View Scheme

D-gulose (4205-23-6) → Diacetone D-glucose (2595-05-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: zinc(II) chloride / Inert atmosphere; Schlenk technique 2: chromium(VI) oxide; acetic anhydride; pyridine / Inert atmosphere; Schlenk technique 3: sodium tetrahydroborate / ethanol; water / 3 h / 0 °C / Inert atmosphere; Schlenk technique View Scheme

3-deoxy-1,2;5,6-di-O-isopropylidene-α-D-glucofuranoside (4613-62-1) → Diacetone D-glucose (2595-05-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: oxalyl dichloride; triethylamine / dichloromethane; dimethyl sulfoxide / -78 - 20 °C 2: sodium tetrahydroborate; water / ethanol / 1 h / 0 °C View Scheme

D-glucose (50-99-7) → Diacetone D-glucose (2595-05-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: sulfuric acid 2: oxalyl dichloride; triethylamine / dichloromethane; dimethyl sulfoxide / -78 - 20 °C 3: sodium tetrahydroborate; water / ethanol / 1 h / 0 °C View Scheme
Multi-step reaction with 2 steps 1: copper(II) sulfate / Acidic conditions 2: acetic anhydride; PDC View Scheme

D-glucofuranose (610-85-5, 7045-51-4, 19217-07-3, 30412-16-9, 34685-37-5, 36468-79-8, 36468-80-1, 36468-81-2, 36468-82-3, 36468-84-5, 36574-15-9, 36574-18-2, 36574-19-3, 36574-21-7, 36972-23-3, 36978-43-5, 37738-80-0, 40461-75-4, 40461-79-8, 40461-80-1, 40461-83-4, 40550-49-0, 41612-82-2, 41846-85-9, 41846-86-0, 41846-87-1, 41846-88-2, 41846-89-3, 41846-90-6, 41846-91-7, 41846-92-8, 41846-93-9, 41846-94-0, 41846-95-1, 41846-96-2, 41846-97-3, 41847-47-6, 41847-48-7, 41847-49-8, 41847-50-1, 41847-62-5, 41847-63-6, 41847-64-7, 41847-65-8, 41847-66-9, 41847-67-0, 41847-68-1, 51076-04-1, 89673-68-7, 131064-93-2, 131064-94-3, 131064-95-4, 131064-96-5, 131064-97-6, 131065-02-6, 131065-03-7, 131065-04-8, 131065-05-9, 131065-06-0) → Diacetone D-glucose (2595-05-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: sulfuric acid 2: phosgene; triethylamine / dichloromethane / 1.5 h / -78 - 20 °C 3: sodium tetrahydroborate; ethanol / water / 1 h / 0 - 20 °C View Scheme
Multi-step reaction with 3 steps 1: zinc(II) chloride; phosphoric acid / 15 - 30 °C / Large scale 2: potassium bromide; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium hypochlorite; sodium hydrogencarbonate / water; ethyl acetate / 0 - 35 °C 3: sodium tetrahydroborate / water / 10 - 15 °C View Scheme

Diacetone D-glucose (2595-05-3) → 1,2-O-isopropylidene-α-D-allofuranose (4495-04-9)

Conditions	Yield
With water; acetic acid at 20℃; for 8h; regioselective reaction;	100%
Stage #1: Diacetone D-glucose With carbon tetrabromide In methanol for 0.5h; Irradiation; Stage #2: In methanol at 20℃; for 14.5h;	90%
With silica supported polyphosphoric acid In acetonitrile at 55℃; for 0.5h;	82%

trifluoromethylsulfonic anhydride (358-23-6) + Diacetone D-glucose (2595-05-3) → 1,2:5,6-di-O-isopropylidene-3-O-trifluoromethanesulfonyl-α-D-allofuranose (55951-90-1)

Conditions	Yield
With pyridine In dichloromethane at -30℃; for 0.75h;	100%
With pyridine at 0 - 20℃; Inert atmosphere;	95%
With pyridine at 0 - 20℃; for 3.5h;	92%

5-(1-hydroxyethylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione (85920-63-4) + Diacetone D-glucose (2595-05-3) → (1,2:5,6-di-O-isopropylidene-α-D-allofuranos-3-O-yl) 3-oxobutanoate (342003-61-6)

Conditions	Yield
In toluene for 8h; Heating;	100%

benzyl bromide (100-39-0) + Diacetone D-glucose (2595-05-3) → 1,2:5,6-di-O-isopropylidene-3-O-benzyl-α-D-allofuranose (22331-21-1)

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 20℃; for 8h;	100%
Stage #1: Diacetone D-glucose With sodium hydride In acetonitrile; mineral oil at 0℃; for 1h; Inert atmosphere; Stage #2: benzyl bromide In methanol; acetonitrile; mineral oil at 0℃; for 4.5h;	90%
With sodium hydride	60%

benzoyl cyanide (613-90-1) + Diacetone D-glucose (2595-05-3) → (+)-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-allofuranos-3-yl benzoate (29474-73-5)

Conditions	Yield
With triethylamine In acetonitrile at 0℃;	100%
With triethylamine In acetonitrile at 20℃; for 15h;

tert-butylchlorodiphenylsilane (58479-61-1) + Diacetone D-glucose (2595-05-3) → tert-Butyl-[(3aR,5R,6R,6aR)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yloxy]-diphenyl-silane (378238-89-2)

Conditions	Yield
With 1H-imidazole In N,N-dimethyl-formamide for 18h;	99%

binaphthol chlorophosphite (137156-22-0, 171878-71-0, 155613-52-8) + Diacetone D-glucose (2595-05-3) → 4-[5-(2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yloxy]-3,5-dioxa-4-phospha-cyclohepta[2,1-a;3,4-a']dinaphthalene

Conditions	Yield
With triethylamine In toluene for 16h;	99%
With triethylamine In toluene for 16h;	98%

acetic anhydride (108-24-7) + Diacetone D-glucose (2595-05-3) → 3-O-acetyl-1,2:5,6-di-O-isopropylidene-α-D-allofuranose (29474-72-4)

Conditions	Yield
With iron(III) sulfate at 20℃; for 6h;	99%
With pyridine at 20℃;
With pyridine

pivaloyl chloride (3282-30-2) + Diacetone D-glucose (2595-05-3) → 3-O-(2,2-dimethylpropanoyl)-1,2:5,6-di-O-isopropylidene-α-D-allofuranose

Conditions	Yield
With triethylamine In toluene at 20℃; for 72h;	99%

α-chlorophenylacetyl chloride (2912-62-1) + Diacetone D-glucose (2595-05-3) → 1,2:5,6-di-O-isopropylidene-α-D-allofuranos-3-O-yl α-chloro-α-phenylacetate

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 2h;	99%

2-bromomethylnaphthyl bromide (939-26-4) + Diacetone D-glucose (2595-05-3) → 3-O-(2-naphthylmethyl)-1,2:5,6-di-O-isopropylidene-α-D-allofuranose (956485-06-6)

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 0℃;	99%
With sodium hydride In N,N-dimethyl-formamide for 1.16667h; Cooling with ice;	99%
With sodium hydride In N,N-dimethyl-formamide for 1h; Cooling with ice;	99%

2-bromomethylnaphthyl bromide (939-26-4) + Diacetone D-glucose (2595-05-3) → C23H28O6

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide for 1h; Cooling with ice;	99%

2-Bromopropionic acid (598-72-1) + Diacetone D-glucose (2595-05-3) → 1,2:5,6-di-O-isopropylidene-α-D-allofuranos-3-O-yl α-bromopropionate

Conditions	Yield
With dmap; triethylamine; dicyclohexyl-carbodiimide In dichloromethane at 20℃; for 3h;	98%

Diacetone D-glucose (2595-05-3) + (4-tert-butylphenyl)methanesulfonyl chloride → (4-tert-Butyl-phenyl)-methanesulfonic acid (3aR,5R,6R,6aR)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yl ester (412021-21-7)

Conditions	Yield
With pyridine In dichloromethane at 20℃; for 24h;	97%

isobutyryl chloride (79-30-1) + Diacetone D-glucose (2595-05-3) → 3-O-(2-methylpropanoyl)-1,2:5,6-di-O-isopropylidene-α-D-allofuranose

Conditions	Yield
With triethylamine In toluene at 20℃; for 2h;	97%

hexadecylamine (143-27-1) + 2,4-bis(3,5-di-tert-butyl-4-hydroxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide (58851-58-4) + Diacetone D-glucose (2595-05-3) → C26H41O7PS2*C16H35N

Conditions	Yield
Stage #1: 2,4-bis(3,5-di-tert-butyl-4-hydroxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide; Diacetone D-glucose In benzene at 20℃; for 1h; Inert atmosphere; Stage #2: hexadecylamine In benzene at 20℃; for 1h; Inert atmosphere;	97%

butyryl chloride (141-75-3) + Diacetone D-glucose (2595-05-3) → 3-O-butanoyl-1,2:5,6-di-O-isopropylidene-α-D-allofuranose (120255-67-6)

Conditions	Yield
With triethylamine In toluene at 20℃; for 2h;	96%

(Z)-2-methyl-2-butenoic anhydride (94487-74-8) + Diacetone D-glucose (2595-05-3) → 3-angeloyl-1,2:5,6-O-isopropylidene-allofuranose (1417986-37-8)

Conditions	Yield
With caesium carbonate In acetonitrile at 20℃; for 0.5h;	96%

Diacetone D-glucose (2595-05-3) → (3S)-3-chloro-3-deoxy-1,2:5,6-di-O-isoproplylidene-α-D-allofuranose (32785-94-7)

Conditions	Yield
Stage #1: Diacetone D-glucose With sulfuryl dichloride In dichloromethane at -5 - 0℃; for 0.666667h; Inert atmosphere; Stage #2: With 1,2,3-Benzotriazole In dichloromethane at 20℃; for 6.5h; Inert atmosphere;	96%

trifluoromethylsulfonic anhydride (358-23-6) + Diacetone D-glucose (2595-05-3) → 1,2:5,6-di-O-isopropylidene-3-O-triflyl-α-D-glucofuranose (55951-93-4)

Conditions	Yield
Stage #1: Diacetone D-glucose With pyridine In dichloromethane at 0℃; for 0.166667h; Inert atmosphere; Stage #2: trifluoromethylsulfonic anhydride In dichloromethane at 0℃; Inert atmosphere;	96%

tert-butyldimethylsilyl chloride (18162-48-6) + Diacetone D-glucose (2595-05-3) → 3-O-[(tert-butyl)dimethylsilyl]-1,2:5,6-di-O-isopropylidene-α-D-allofuranose (403737-31-5)

Conditions	Yield
With 1H-imidazole In N,N-dimethyl-formamide for 18h;	95%
With 1H-imidazole In N,N-dimethyl-formamide at 20℃; for 18h; Inert atmosphere;	94%
With 1H-imidazole In N,N-dimethyl-formamide at 20℃; silylation;

benzoyl chloride (98-88-4) + Diacetone D-glucose (2595-05-3) → (+)-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-allofuranos-3-yl benzoate (29474-73-5)

Conditions	Yield
In pyridine at 20℃; for 6h; Acylation;	95%
With pyridine at 20℃; for 20h;	90%
With pyridine at 0 - 20℃; Inert atmosphere;	90%
With pyridine In dichloromethane at 0℃; for 1h;
In pyridine

p-toluenesulfonyl chloride (98-59-9) + Diacetone D-glucose (2595-05-3) → 1,2,5,6-di-O-isopropylidene-3-O-(p-toluenesulfonyl)-α-D-allofuranose (3253-75-6, 13964-21-1, 19131-06-7, 23344-48-1, 26597-75-1, 28140-21-8)

Conditions	Yield
With pyridine at 20℃; Tosylation;	95%
With pyridine	91.6%
With pyridine at 0 - 20℃;	66%
With pyridine; dmap at 20℃; for 48h;	57%
With pyridine; dmap In dichloromethane at 0 - 20℃; for 12h; Product distribution / selectivity;

Diacetone D-glucose (2595-05-3) → 3-deoxy-1,2;5,6-di-O-isopropylidene-3-fluoro-α-D-glucofuranose (14049-05-9)

Conditions	Yield
With pyridine In dichloromethane; toluene at -78 - 40℃; for 168h;	95%
With (bis-(2-methoxyethyl)amino)sulfur trufluoride In dichloromethane; toluene at -78 - 40℃; for 168h;	95%
With potassium fluoride; 1,3-bis(2,6-diisopropylphenyl)-2,2-difluoro-2,3-dihydro-1h-imidazole; N-ethyl-N,N-diisopropylamine In toluene at 80℃; for 16h; Inert atmosphere;	83%

2-chloroethyl methyl ether (627-42-9) + Diacetone D-glucose (2595-05-3) → 1,2:5,6-di-O-isopropyliden-3-O-(2-methoxyethyl)-α-D-allofuranose (553664-29-2)

Conditions	Yield
With potassium hydroxide In dimethyl sulfoxide at 55℃; for 7.5h;	95%

allyl bromide (106-95-6) + Diacetone D-glucose (2595-05-3) → 1,2:5,6-di-O-isopropylidene-3-O-allyl-α-D-allofuranose (33746-39-3)

Conditions	Yield
With sodium hydroxide; tetrabutylammomium bromide In dichloromethane; water at 25℃; for 2h;	95%
With sodium hydroxide; tetra-(n-butyl)ammonium iodide In dichloromethane; water at 23℃; for 5h;	92%
With sodium hydride In N,N-dimethyl-formamide at 20℃; for 3h;
With tetra-(n-butyl)ammonium iodide; sodium hydroxide In dichloromethane; water at 23℃; for 5h;

isopropyl 2-bromoacetate (29921-57-1) + Diacetone D-glucose (2595-05-3) → [(3aR,5R,6R,6aR)-5-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yloxy]-acetic acid isopropyl ester

Conditions	Yield
With 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphorine In tetrahydrofuran at 0 - 20℃; for 48h;	95%

2,3,4,6-tetra-O-benzoyl-D-glucopyranosyl trichloroacetimidate (149707-75-5) + Diacetone D-glucose (2595-05-3) → 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl-(1->3)-1,2:5,6-di-O-isopropylidene-α-D-allofuranose (1138333-94-4)

Conditions	Yield
With trimethylsilyl trifluoromethanesulfonate In dichloromethane at 20℃; for 4h; Molecular sieve; Inert atmosphere;	94%

Upstream product

• 921-60-8 L-glucose 
• 67-64-1 acetone 
• 121701-18-6 1,2-O-isopropylidene-α-L-glucofuranose 
• 6027-42-5 (2S,3S,4S)-6-Nitro-hexane-1,2,3,4,5-pentaol 
• 1990-29-0 D-altrose 
• 41846-94-0 D-altrose 
• 2280-44-6 D-Glucose 
• 50-99-7 D-glucose 
• 77-76-9 2,2-dimethoxy-propane 
• 16713-80-7 Acetic acid (3aR,5S,6R,6aR)-5-(2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yl ester 
• 26623-16-5 1,2:5,6-di-O-isopropylidene-β-D-arabino-hexofuranos-3-ulose 
• 29586-98-9 3-O-acetyl-1,2,5,6-di-isopropylidene-α-D-glucofuranose 
• 582-52-5 1,2:5,6-Di-O-isopropylidene-β-D-altrofuranose 
• 2847-00-9 1,2:5,6-di-O-isopropylidene-α-D-hexofuran-3-ulose 

Downstream Products

• 131791-66-7 Acetic acid (2R,3R,4S,5R,6S)-3,4,5-tris-benzyloxy-6-[(3aS,5S,6R,6aS)-5-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yloxy]-tetrahydro-pyran-2-ylmethyl ester 
• 131791-64-5 Acetic acid (2R,3R,4S,5R,6R)-3,4,5-tris-benzyloxy-6-[(3aS,5S,6R,6aS)-5-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yloxy]-tetrahydro-pyran-2-ylmethyl ester 
• 19189-62-9 Thiocarbonic acid O-[(3aS,5S,6R,6aS)-5-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yl] ester O-phenyl ester 
• 714967-70-1 3-O-acetyl-1,2-O-isopropylidene-6-O-trityl-α-L-glucofuranose 
• 90941-98-3 (S)-2-Benzenesulfinyl-3-[(4S,6S)-6-(2-benzyloxy-ethyl)-2,2-dimethyl-[1,3]dioxan-4-yl]-1-[(4R,6S)-6-(tert-butyl-dimethyl-silanyloxymethyl)-2,2-dimethyl-[1,3]dioxan-4-yl]-propan-1-ol 
• 90941-85-8 (S)-2-Benzenesulfinyl-1-[(4R,6S)-6-(tert-butyl-dimethyl-silanyloxymethyl)-2,2-dimethyl-[1,3]dioxan-4-yl]-ethanol 
• 90941-83-6 (R)-3-[(4R,6S)-6-(2-Benzyloxy-ethyl)-2,2-dimethyl-[1,3]dioxan-4-yl]-1-[(4R,6S)-6-(tert-butyl-dimethyl-silanyloxymethyl)-2,2-dimethyl-[1,3]dioxan-4-yl]-propan-1-ol 
• 90941-83-6 (S)-3-[(4R,6S)-6-(2-Benzyloxy-ethyl)-2,2-dimethyl-[1,3]dioxan-4-yl]-1-[(4R,6S)-6-(tert-butyl-dimethyl-silanyloxymethyl)-2,2-dimethyl-[1,3]dioxan-4-yl]-propan-1-ol 
• 4118-60-9 O¹,O²-isopropyliden-5,6-anhydro-α-L-glucofuranose 
• 121613-69-2 O¹,O²-isopropylidene-O⁶-(toluene-4-sulfonyl)-α-L-glucofuranose 
• 1372631-32-7 3-O-benzyl-1,2;5,6-di-O-isopropylidene-α-L-glucofuranose 
• 1372631-90-7 N-benzyl-6-O-(tert-butyldimethylsilyl)-3,5-dideoxy-3,5-imino-1,2-O-isopropylidene-β-D-idofuranose 
• 1372632-04-6 N-benzyl-2,4-dideoxy-2,4-imino-D-iditol 

Relevant academic research and scientific papers

Microwave-assisted Synthesis of Hybrid Heterocyclics as Biological Potent Molecules

A series of novel 5-((1H-benzo[d]imidazol-2-yl)methyl)-2-((3aR,5S,6S,6aR)-2,2-dimethyl-6-((1-phenyl-1H-1,2,3-triazol-4-yl)methoxy)tetrahydrofuro[2,3-d][1,3]dioxol-5-yl)-3-phenylthiazolidin-4-ones 9a–n has been synthesized from triazole-linked thiazolidinone derivatives 8a–g with o-phenylenediamine and characterized by IR, NMR, MS, and elemental analyses. Further, these compounds were screened for their antibacterial activity against Gram-positive bacteria, namely, Bacillus subtilis (ATCC 6633), Staphylococcus aureus (ATCC 6538p), and Micrococcus luteus (IFC 12708), and Gram-negative bacteria, namely, Proteus vulgaris (ATCC 3851), Salmonella typhimurium (ATCC 14028), and Escherichia coli (ATCC 25922). Among the screened compounds, compounds 9b, 9d, 9h, and 9i are highly active against almost all selected bacterial strains; the remaining compounds showed moderate to good activity and emerged as potential molecules for further development.

Synthesis and In Vitro Study of Hybrid Heterocyclic's as Potential Nematicidal Agents

A series of novel 5-((3aR,5S,6S,6aR)-6-((1-(4-chlorophenyl)-1H-1,2,3-triazol-4-yl)methoxy)-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-5-yl)-3-(4-fluorophenyl)-6-phenyl-3,3a,5,6-tetrahydroisoxazolo[3,4-d]thiazoles 10a–g were synthesized by the reaction of chalcone derivatives of 2-((3aR,5S,6S,6aR)-6-((1-(4-chlorophenyl)-1H-1,2,3-triazol-4-yl)methoxy)-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-5-yl)-3-phenylthiazolidin-4-one 9 with hydroxylamine hydrochloride. The chemical structures of newly synthesized compounds were elucidated by IR, NMR, MS, and elemental analysis. The compounds 10 a–g were evaluated for their nematicidal activity against Dietylenchus myceliophagus and Caenorhabditis elegans; compound 10e and 10f showed appreciable nematicidal activity. Further, the compounds 10a – g were screened for their antifungal activity against Candida albicans (ATCC 10231), Aspergillus fumigates (HIC 6094), Trichophyton rubrum (IFO 9185), and Trichopyton mentagrophytes (IFO 40996). The compounds 10b and 10f displayed notable antifungal activity against all the microorganisms employed. The activity of these compounds is almost equal to the standard. It is also interesting to note that the compounds 10b and 10f and 10g showed activity towards C. albicans at the concentration of 3.75?μM, which is less than the concentration of the standard Amphotericin B.

Mechanistic Investigation of 1,2-Diol Dehydration of Paromamine Catalyzed by the Radical S-Adenosyl- l -methionine Enzyme AprD4

AprD4 is a radical S-adenosyl-l-methionine (SAM) enzyme catalyzing C3′-deoxygenation of paromamine to form 4′-oxo-lividamine. It is the only 1,2-diol dehydratase in the radical SAM enzyme superfamily that has been identified and characterized in vitro. The AprD4 catalyzed 1,2-diol dehydration is a key step in the biosynthesis of several C3′-deoxy-aminoglycosides. While the regiochemistry of the hydrogen atom abstraction catalyzed by AprD4 has been established, the mechanism of the subsequent chemical transformation remains not fully understood. To investigate the mechanism, several substrate analogues were synthesized and their fates upon incubation with AprD4 were analyzed. The results support a mechanism involving formation of a ketyl radical intermediate followed by direct elimination of the C3′-hydroxyl group rather than that of a gem-diol intermediate generated via 1,2-migration of the C3′-hydroxyl group to C4′. The stereochemistry of hydrogen atom incorporation after radical-mediated dehydration was also established.

TLR7 AGONISTS

The present invention relates to TLR7 agonists according to Formula I and their use in the treatment of diseases such as cancer and infectious disease.

Triethylamine-methanol mediated selective removal of oxophenylacetyl ester in saccharides

A highly selective, mild, and efficient method for the cleavage of oxophenylacetyl ester protected saccharides was developed using triethylamine in methanol at room temperature. The reagent proved successful against different labile groups like acetal, ketal, and PMB and also generated good yields of the desired saccharides bearing lipid esters. Further, we also observed DBU in methanol as an alternative reagent for the deprotection of acetyl, benzoyl, and oxophenylacetyl ester groups. This journal is

A method for preparing N-alkylated kanosamines from diacetone D-glucose

The aminoglycoside (AG) antibiotics have seen a resurgence in their clinical use given the increase in multi drug resistant bacterial infections. Campaigns to generate novel analogs show promise that structural modification can lead to compounds with improved pharmacological properties. The results described herein include a new method to synthesize mono-, di-, and mixed N-alkylated kanosamine sugars and their elaboration into novel glycosides that inhibit bacterial protein synthesis in vitro.

NOVEL PROCESS FOR MAKING ALLOFURANOSE FROM GLUCOFURANOSE

The present invention relates to the manufacture of allofuranose from glucofuranose as defined in the description and in the claim. Allofuranos is an intermediate in the manufacture of oligonucleotides which can be used as a medicament.

Palladium-Catalyzed One-Pot Stereospecific Synthesis of 2-Deoxy Aryl C-Glycosides from Glycals and Anilines in the Presence of tert-Butyl Nitrite

The palladium-catalyzed one-pot synthesis of 2,3-deoxy-3-keto aryl C-glycosides is achieved from glycals and anilines in the presence of tert-butyl nitrite and aqueous HBF 4 under mild conditions. This one-pot method stereospecifically provides α-and β-Aryl glycosides (≥19:1 by NMR) in good yields at room temperature. The configuration at the C-3 position in the glycal determines the anomeric selectivity (i.e., α or β) of the desired products.

GLUCOSIDE MONOMER, POLYMERIZATION COMPOSITION COMPRISING THE SAME AND HYDROGEL LENS USING THE SAME

The present invention relates to a glucoside-based monomer represented by chemical formula 1, a polymeric composition for producing hydrogel comprising the same, and a hydrogel lens using the same. In the chemical formula 1, R_1 to R_4 is hydrogen, an alkyl group of C_1-C_4, or AA, R_6 is hydrogen or an alkyl group of C_1-C_4, at least one of the R_1 to R_4 is BB, R_5 is selected from hydrogen or CC, and m is an integer selected from 0 to 10. According to the present invention, hydrogel lenses having improved wettability can be provided.COPYRIGHT KIPO 2019

Synthesis, photophysical properties, and photodynamic activity of positional isomers of TFPP-glucose conjugates

The synthesis and characterization of a ‘complete set’ of positional isomers of tetrakis(perfluorophenyl)porphyrins (TFPP)-glucose conjugates (1OH, 2OH, 3OH, 4OH, and 6OH) are reported herein. The cellular uptake and photocytotoxicity of these conjugates were examined in order to investigate the influence of location of the TFPP moiety on the D-glucose molecule on the biological activity of the conjugates. An In vitro biological evaluation revealed that the certain of these isomers have a greater effect on cellular uptake and cytotoxicity than others. The TFPP-glucose conjugates 1OH, 3OH, and 4OH were found to exert exceptional photocytotoxicity in several types of cancer cells compared to 2OH and 6OH substituted isomers.