2595-05-3

Basic information

• Product Name: 1,2:5,6-Di-O-isopropylidene-alpha-D-allofuranose
• Synonyms: 1,2:5,6-Di-O-isopropylidene-alpha-D-allo;1,2:5,6-Di-O-isoprop;1,2:5,6-Di-O-isopropylidene-α-D-allofuranose ,98%;1,2:5,6-Bis-O-(1-Methylethylidene)-α-D-allofuranose;1,2:5,6-Diacetone-D-allofuranose;Diacetone-D-allofuranose;1,2:5,6-Di-O-isopropylidene-alpha-D-ribo-hexofuranose;1,2:5,6-bis-O-(1-Methylethylidene)-alpha-D-Allofuranose
• CAS NO: 2595-05-3
• Molecular Formula: C₁₂H₂₀O₆
• Molecular Weight: 260.28
• Product Categories: Sugars, Carbohydrates & Glucosides;13C & 2H Sugars;Allose;Biochemistry;O-Substituted Sugars;Sugars;Carbohydrates & Derivatives;Carbohydrate Synthesis;Monosaccharides;Specialty Synthesis
• Mol File: 2595-05-3.mol
• Article Data: 66

Chemical Properties

• Melting Point: 73-76 °C(lit.)
• Boiling Point: 363.54°C (rough estimate)
• Flash Point: 173.187 °C
• Appearance: White to off-white/Powder
• Density: 1.2377 (rough estimate)
• Vapor Pressure: 9.94E-07mmHg at 25°C
• Refractive Index: 36.5 ° (C=1, CHCl3)
• Storage Temp.: 2-8°C
• Solubility: almost transparency in Toluene
• PKA: 13.15±0.60(Predicted)
• Stability: Acid Sensitive
• CAS DataBase Reference: 1,2:5,6-Di-O-isopropylidene-alpha-D-allofuranose(CAS DataBase Reference)
• NIST Chemistry Reference: 1,2:5,6-Di-O-isopropylidene-alpha-D-allofuranose(2595-05-3)
• EPA Substance Registry System: 1,2:5,6-Di-O-isopropylidene-alpha-D-allofuranose(2595-05-3)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 22-24/25-36/37-26
• WGK Germany: 3
• F: 21
• Hazardous Substances Data: 2595-05-3(Hazardous Substances Data)

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 
• 1990-29-0 D-altrose 
• 2280-44-6 D-Glucose 
• 67-64-1 acetone 
• 29586-98-9 3-O-acetyl-1,2,5,6-di-isopropylidene-α-D-glucofuranose 
• 2847-00-9 1,2:5,6-di-O-isopropylidene-α-D-hexofuran-3-ulose 
• 50-99-7 D-glucose 
• 4613-62-1 3-deoxy-1,2;5,6-di-O-isopropylidene-α-D-glucofuranoside 
• 4205-23-6 D-gulose 
• 492-62-6 alpha-D-glucopyranose 
• 582-52-5 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose 
• 226943-66-4 3-O-(4,4'-dimethoxytrityl)-1,2:5,6-di-O-isopropylidene-α-D-allofuranose 
• 226943-46-0 3-O-tetrahydropyranyl-1,2:5,6-di-O-isopropylidene-α-D-allofuranose 
• 582-52-5 1,2:5,6-Di-O-isopropylidene-β-D-altrofuranose 

Downstream Products

• 7757-38-2 2,3,5,6-di-O-isopropylidene-D-mannofuranose 
• 13964-23-3 3-azido-3-deoxy-1,2:5,6-di-(O-isopropylidene)-α-D-glucofuranose 
• 63846-98-0 1,2-O-(1-Methylethylidene)-α-D-ribo-pentodialdo-1,4-furanose 
• 412021-21-7 (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 
• 872676-56-7 (3-Methoxy-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 
• 29587-01-7 5-[2,2-dimethyl-(4R)-1,3-dioxolan-4-yl]-2,2-dimethyl-(3aR,5R,6R,6aR)-perhydrofuro[2,3-d][1,3]dioxol-6-yl methyl ether 
• 934339-35-2 3-O-benzoyl-6-deoxy-6-diethylphosphono-1,2-O-isopropylidene-D-allofuranose 
• 934339-33-0 5-O-acetyl-3-O-benzoyl-6-deoxy-6-iodo-1,2-O-isopropylidene-D-allofuranose 
• 31795-13-8 3-O-benzoyl-1,2-O-isopropylidene-α-D-allofuranose 
• 143504-31-8 3-O-Benzoyl-6-deoxy-6-iodo-1,2-O-isopropylidene-α-D-allofuranose 
• 159043-21-7 3-O-Benzoyl-1,2-O-isopropyliden-6-O-(p-tolylsulfonyl)-α-D-allofuranose 
• 582-52-5 1,2:5,6-Di-O-isopropylidene-α-D-glucofuranose 
• 69940-02-9 3-O-(4-Methoxybenzyl)-1,2:5,6-di-O-isopropylidene-α-D-allofuranose 
• 417703-00-5 (3aR,5R,6R,6aR)-6-(2-bromo-benzyloxy)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydrofuro[2,3-d][1,3]dioxole 

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