68733-20-0

Basic information

• Product Name: 1,3,4,6-TETRA-O-ACETYL-2-AZIDO-2-DEOXY-ALPHA-D-MANNOPYRANOSE
• Synonyms: 2-AZIDO-2-DEOXY-1,3,4,6-TETRA-O-ACETYL-ALPHA-D-MANNOPYRANOSE;1,3,4,6-TETRA-O-ACETYL-2-AZIDO-2-DEOXY-ALPHA-D-MANNOPYRANOSE;Tetraacetylazidodeoxymannopyranose;1,3,4,6-Tetra-O-acetyl-2-azido-2-deoxy-a-D-mannopyranose;2-AZIDO-2-DEOXY-1,3,4,6-TETRA-O-ACETYL-A-D-MANNOPYRANOSE;1,3,4,6-Tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranose ,98%;-D-mannopyranose;1,3,4,6-Tetra-O-acetyl-2-azido-2-deoxy-&alpha
• CAS NO: 68733-20-0
• Molecular Formula: C₁₄H₁₉N₃O₉
• Molecular Weight: 373.32
• Product Categories: Biochemistry;O-Substituted Sugars;Sugars
• Mol File: 68733-20-0.mol
• Article Data: 14

Chemical Properties

• Melting Point: 132 °C
• Appearance: /
• Storage Temp.: Refrigerator
• CAS DataBase Reference: 1,3,4,6-TETRA-O-ACETYL-2-AZIDO-2-DEOXY-ALPHA-D-MANNOPYRANOSE(CAS DataBase Reference)
• NIST Chemistry Reference: 1,3,4,6-TETRA-O-ACETYL-2-AZIDO-2-DEOXY-ALPHA-D-MANNOPYRANOSE(68733-20-0)
• EPA Substance Registry System: 1,3,4,6-TETRA-O-ACETYL-2-AZIDO-2-DEOXY-ALPHA-D-MANNOPYRANOSE(68733-20-0)

Safety Data

• Hazardous Substances Data: 68733-20-0(Hazardous Substances Data)

Usage

Description

1,3,4,6-Tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranose is an analog of N-acetylmannosamine (ManNAc) and a building block. It has been used as a precursor in the synthesis of differently substituted trimers of the group A N. meningitidis capsular polysaccharide repeating unit for use in immunological experiments. It has also been used in the synthesis of fluorescent probes for lysosomal labeling.

InChI:InChI=1/C14H19N3O9/c1-6(18)22-5-10-12(23-7(2)19)13(24-8(3)20)11(16-17-15)14(26-10)25-9(4)21/h10-14H,5H2,1-4H3/t10-,11+,12-,13-,14+/m1/s1

Synthetic route

acetic anhydride (108-24-7) + methyl 3-O-acetyl-2-azido-4,6-O-benzylidene-2-deoxy-α-D-mannopyranoside (115945-97-6) → 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0)

Conditions	Yield
With sulfuric acid at 0℃; for 1h;	92%

acetic anhydride (108-24-7) + (4aR,6S,7S,8R,8aS)-7-azido-6-methoxy-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-8-ol → 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0)

Conditions	Yield
With sulfuric acid at 20℃; for 2h;	82%

acetic anhydride (108-24-7) + Methyl 2-azido-2-deoxy-4,6-O-(phenylmethylene)-α-D-mannopyranoside (116003-78-2) → 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0)

Conditions	Yield
With sulfuric acid at 20℃; for 2.5h;	78%
With sulfuric acid at 20℃; for 0.666667h;	75%

mercury(II) diacetate (1600-27-7) + D-glucal triacetate (2873-29-2) → 2-azido-2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranosyl acetate (56883-33-1) + 1,3,4,6-Tetra-O-acetyl-2-azido-2-deoxy-β-D-glucopyranose (80321-89-7) + Acetic acid (2R,3R,4S,5R,6S)-4-acetoxy-2-acetoxymethyl-6-azido-5-chloro-tetrahydro-pyran-3-yl ester + 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0)

Conditions	Yield
With chlorine azide In tetrachloromethane at 0℃; for 1h; Product distribution; Irradiation; other halogen-azide, in other solvents under irradiation or in the dark, various time and temperature;	A 9% B 62% C 8% D 11%
With chlorine azide 1.) CCl4, irrad., 0 deg C, 1 h; 2.) glacial acetic acid, room temp.; Yield given. Multistep reaction;	A n/a B 62% C 8% D 11%
With chlorine azide 1.) CCl4, irrad., 0 deg C, 1 h; 2.) glacial acetic acid, room temp.; Yield given. Multistep reaction;	A 9% B 62% C 8% D n/a
With chlorine azide 1.) CCl4, irrad., 0 deg C, 1 h, 2.) glacial acetic acid, room temp.; Yield given. Multistep reaction;	A 9% B n/a C 8% D 11%

1,3,4,6-tetra-O-acetyl-2-O-trifluoromethanesulfonyl-α-D-glucopyranose (113544-40-4) → 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0)

Conditions	Yield
With sodium azide In N,N-dimethyl-formamide at 60℃; for 0.5h;	58%
With sodium azide In N,N-dimethyl-formamide	20%
With sodium azide In N,N-dimethyl-formamide at 60℃; for 5h;	10%

sodium acetate (127-09-3) + Acetic acid (2R,3S,4R)-4-acetoxy-2-acetoxymethyl-5-azido-6-nitrooxy-tetrahydro-pyran-3-yl ester (668481-16-1) → 2-azido-2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranosyl acetate (56883-33-1) + 1,3,4,6-Tetra-O-acetyl-2-azido-2-deoxy-β-D-glucopyranose (80321-89-7) + 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0)

Conditions	Yield
In acetic acid at 100℃; for 1h;	A n/a B n/a C 17%

sodium acetate (127-09-3) + D-glucal triacetate (2873-29-2) → 2-azido-2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranosyl acetate (56883-33-1) + 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0)

Conditions	Yield
With sodium azide; ammonium cerium(IV) nitrate 1.) EtOAc, CH3CN, -40 deg C, 6 d; 2.) glacial acetic acid, 100 deg C, 1 h; Yield given. Multistep reaction. Yields of byproduct given;

sodium acetate (127-09-3) + D-glucal triacetate (2873-29-2) → 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0)

Conditions	Yield
With sodium azide; ammonium cerium(IV) nitrate 1.) acetonitrile, ethylacetate, -40 deg C; Yield given. Multistep reaction;

1,3,4,6-tetra-O-acetyl glucopyranose (4692-12-0) → 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 97 percent / pyridine / CH2Cl2 / 1 h / -20 °C 2: 58 percent / NaN3 / dimethylformamide / 0.5 h / 60 °C View Scheme
Multi-step reaction with 2 steps 1: 66 percent / pyridine; CH2Cl2 / 1.5 h / 3 °C 2: 10 percent / NaN3 / dimethylformamide / 5 h / 60 °C View Scheme

methyl 4,6-O-benzylidene-α-D-glucopyranoside (3162-96-7) → 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: pyridine / dichloromethane / 3 h / -78 - 20 °C 2: sodium azide / N,N-dimethyl-formamide / 2 h / 80 °C 3: sulfuric acid / 2 h / 20 °C View Scheme

methyl-alpha-D-glucopyranoside (97-30-3) → 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0)

Conditions	Yield
Multi-step reaction with 4 steps 1: 1,3,5-trichloro-2,4,6-triazine / acetonitrile / 1 h / 20 °C / Sonication 2: pyridine / dichloromethane / 3 h / -78 - 20 °C 3: sodium azide / N,N-dimethyl-formamide / 2 h / 80 °C 4: sulfuric acid / 2 h / 20 °C View Scheme

D-mannosamine hydrochloride (4710-95-6, 6730-09-2, 14131-59-0, 14131-62-5, 14131-63-6, 14131-65-8, 14131-67-0, 14257-79-5, 19124-46-0, 20706-90-5, 91673-92-6) + acetic anhydride (108-24-7) → 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) + 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-β-D-mannopyranose (635292-85-2)

Conditions	Yield
Stage #1: D-mannosamine hydrochloride With copper(ll) sulfate pentahydrate; 3-azidosulfonyl-3H-imidazole-1-ium hydrogen sulfate; potassium carbonate In methanol; water at -20 - 20℃; for 6h; Stage #2: acetic anhydride With pyridine at 0 - 20℃; Overall yield = 92 percent; Overall yield = 1.9 g;

4,6-O-benzylidene-1-O-methyl-2-O-trifluoromethylsulfonate-α-D-glucopyranoside (129217-24-9) → 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: sodium azide / N,N-dimethyl-formamide / 12 h / 75 °C 2: sulfuric acid / 4 h / 0 - 20 °C / Inert atmosphere View Scheme

acetic anhydride (108-24-7) + Methyl 2-azido-2-deoxy-4,6-O-(phenylmethylene)-α-D-mannopyranoside (116003-78-2) → 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) + 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-β-D-mannopyranose (635292-85-2)

Conditions	Yield
With sulfuric acid at 0 - 20℃; for 4h; Inert atmosphere; Overall yield = 80 percent; Overall yield = 0.74 g;	A n/a B n/a

4,6-O-benzylidene-1-O-methyl-α-D-glucopyranoside (3162-96-7) → 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: pyridine / dichloromethane / 3 h / -30 °C / Inert atmosphere; Molecular sieve 2: sodium azide / N,N-dimethyl-formamide / 12 h / 75 °C 3: sulfuric acid / 4 h / 0 - 20 °C / Inert atmosphere View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → 3,4,6-Tri-O-acetyl-2-azido-2-deoxy-α-D-mannopyranosyl bromide (95451-93-7)

Conditions	Yield
With titanium(IV) bromide In dichloromethane; ethyl acetate for 144h;	98%
With titanium(IV) bromide In dichloromethane; ethyl acetate at 20℃; for 48h;	93%
With titanium(IV) bromide

ferroceneacetylene (1271-47-2) + 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → 2-deoxy-2-(4-ferrocenyl-1H-1,2,3-triazol-1-yl)-1,3,4,6-tetra-O-acetyl-α-D-mannopyranose

Conditions	Yield
With C60H90N10O30; copper(II) sulfate; sodium L-ascorbate In methanol; dichloromethane; water at 60℃; for 1h; Reagent/catalyst;	95%

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → 3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-mannopyranose (94715-67-0)

Conditions	Yield
With dimethyl amine In tetrahydrofuran at 0 - 20℃;	87%
With hydrazinium monoacetate In N,N-dimethyl-formamide at 20℃; for 1h; Reduction;

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) + para-thiocresol (106-45-6) → p-methylphenyl 2-deoxy-2-azido-3,4,6-tri-O-acetyl-1-thio-D-mannopyranoside (765308-75-6)

Conditions	Yield
With boron trifluoride diethyl etherate In dichloromethane at 20 - 30℃; for 48h; Inert atmosphere;	82%

4-nitro-phenol (100-02-7) + 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → 4-nitrophenyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (570412-04-3)

Conditions	Yield
With zinc(II) chloride at 120℃; for 0.416667h;	70%
With 4 A molecular sieve; boron trifluoride diethyl etherate In dichloromethane at 0℃;	30%

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) + ethanethiol (75-08-1) → ethyl 2-azido-3,4,6-tri-O-acetyl-2-deoxy-1-thio-α-D-mannopyranoside (402831-54-3)

Conditions	Yield
With 4 A molecular sieve; boron trifluoride diethyl etherate In dichloromethane for 7h;	68%
Stage #1: 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside; ethanethiol With MS (4A) In dichloromethane at 20℃; for 0.5h; Stage #2: With boron trifluoride diethyl etherate In dichloromethane for 8h;	68%
With boron trifluoride diethyl etherate In dichloromethane at 0 - 20℃; for 16h; Inert atmosphere;	58%

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → 2-Azido-2-desoxy-β-D-mannopyranose + 2-Azido-2-desoxy-α-D-mannopyranose

Conditions	Yield
With hydrogenchloride; water In methanol for 12h; Ambient temperature; Title compound not separated from byproducts;

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → ethyl 3,4-di-O-acetyl-2-azido-2-deoxy-1-thio-α-D-mannopyranoside (870074-19-4)

Conditions	Yield
Multi-step reaction with 5 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C 4: 75 percent / triethylamine tris(hydrogen fluoride) / tetrahydrofuran / 20 °C View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → (2R,3S,4R,5S,6R)-5-Azido-2-(tert-butyl-dimethyl-silanyloxymethyl)-6-ethylsulfanyl-tetrahydro-pyran-3,4-diol

Conditions	Yield
Multi-step reaction with 3 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → 3,4-di-O-acetyl-2-azido-6-O-(tert-butyldimethylsilyl)-2-deoxy-α-D-mannopyranoside (870074-02-5)

Conditions	Yield
Multi-step reaction with 5 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C 4: 82 percent / N-iodosuccinimide; AgOTf / CH2Cl2 / 0.5 h / -20 °C View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → ethyl 3,4-di-O-acetyl-2-azido-6-O-(tert-butyldimethylsilyl)-2-deoxy-1-thio-α-D-mannopyranoside (870073-99-7)

Conditions	Yield
Multi-step reaction with 4 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → 2-(benzyloxycarbonyl)aminoethyl 3,4-di-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (870074-01-4)

Conditions	Yield
Multi-step reaction with 6 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C 4: 86 percent / 4 Angstroem molecular sieves; N-iodosuccinimide; AgOTf / CH2Cl2 / 0.5 h 5: 97 percent / triethylamine tris(hydrogen fluoride) / tetrahydrofuran / 20 °C View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → 3,4-di-O-acetyl-2-azido-2-deoxy-6-O-dibenzyloxyphosphoryl-α-D-mannopyranoside (870074-21-8)

Conditions	Yield
Multi-step reaction with 8 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C 4: 75 percent / triethylamine tris(hydrogen fluoride) / tetrahydrofuran / 20 °C 5: tetrazole / CH2Cl2 / 0.5 h / 20 °C 6: 200 mg / m-CPBA / CH2Cl2 / 0.5 h / 0 °C 7: 79 percent / N-iodosuccinimide; aq. AgOTf / CH2Cl2 / 0.5 h / -20 °C View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → Acetic acid (2R,3S,4R,5S,6R)-4-acetoxy-5-azido-2-(bis-benzyloxy-phosphanyloxymethyl)-6-ethylsulfanyl-tetrahydro-pyran-3-yl ester

Conditions	Yield
Multi-step reaction with 6 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C 4: 75 percent / triethylamine tris(hydrogen fluoride) / tetrahydrofuran / 20 °C 5: tetrazole / CH2Cl2 / 0.5 h / 20 °C View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → ethyl 3,4-di-O-acetyl-2-azido-2-deoxy-6-O-dibenzyloxyphosphoryl-1-thio-α-D-mannopyranoside (870074-20-7)

Conditions	Yield
Multi-step reaction with 7 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C 4: 75 percent / triethylamine tris(hydrogen fluoride) / tetrahydrofuran / 20 °C 5: tetrazole / CH2Cl2 / 0.5 h / 20 °C 6: 200 mg / m-CPBA / CH2Cl2 / 0.5 h / 0 °C View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → 2-(benzyloxycarbonyl)aminoethyl 3,4-di-O-acetyl-2-azido-6-O-(tert-butyldimethylsilyl)-2-deoxy-α-D-mannopyranoside (870074-00-3)

Conditions	Yield
Multi-step reaction with 5 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C 4: 86 percent / 4 Angstroem molecular sieves; N-iodosuccinimide; AgOTf / CH2Cl2 / 0.5 h View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → 3,4-di-O-acetyl-2-azido-6-O-(tert-butyldimethylsilyl)-2-deoxy-α-D-mannopyranosyl hydrogen-phosphonate triethylammonium salt

Conditions	Yield
Multi-step reaction with 6 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C 4: 82 percent / N-iodosuccinimide; AgOTf / CH2Cl2 / 0.5 h / -20 °C 5: 97 percent / imidazole; PCl3 / acetonitrile / 0.17 h / 20 °C View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → 3,4-di-O-acetyl-2-azido-2-deoxy-6-O-dibenzyloxyphosphoryl-α-D-mannopyranosyl hydrogenphosphonate triethylammonium salt

Conditions

Yield

Multi-step reaction with 9 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C 4: 75 percent / triethylamine tris(hydrogen fluoride) / tetrahydrofuran / 20 °C 5: tetrazole / CH2Cl2 / 0.5 h / 20 °C 6: 200 mg / m-CPBA / CH2Cl2 / 0.5 h / 0 °C 7: 79 percent / N-iodosuccinimide; aq. AgOTf / CH2Cl2 / 0.5 h / -20 °C 8: 92 percent / imidazole; PCl3 / acetonitrile / 0.17 h / 20 °C View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → C36H54N7O17PSi*C6H15N

Conditions	Yield
Multi-step reaction with 7 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C 4: 82 percent / N-iodosuccinimide; AgOTf / CH2Cl2 / 0.5 h / -20 °C 5: 97 percent / imidazole; PCl3 / acetonitrile / 0.17 h / 20 °C 6: pivaloyl chloride; pyridine / 1 h / 20 °C View Scheme
Multi-step reaction with 7 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C 4: 86 percent / 4 Angstroem molecular sieves; N-iodosuccinimide; AgOTf / CH2Cl2 / 0.5 h 5: 97 percent / triethylamine tris(hydrogen fluoride) / tetrahydrofuran / 20 °C 6: pivaloyl chloride; pyridine / 1 h / 20 °C View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → 2-aminoethyl (2-acetamido-3,4-di-O-acetyl-2-deoxy-α-D-mannopyranosyl phosphate)-(1->6)-(2-acetamido-3,4-di-O-acetyl-2-deoxy-α-D-mannopyranosyl phosphate)-(1->6)-(2-acetamido-3,4-di-O-acetyl-2-deoxy-α-D-mannopyranoside) bis-triethylammonium salt

Conditions

Yield

Multi-step reaction with 12 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C 4: 82 percent / N-iodosuccinimide; AgOTf / CH2Cl2 / 0.5 h / -20 °C 5: 97 percent / imidazole; PCl3 / acetonitrile / 0.17 h / 20 °C 6: pivaloyl chloride; pyridine / 2 h 7: 351 mg / aq. I2; pyridine / -40 - -10 °C 8: NiCl2(H2O)6; NaBH4 / methanol / 0 °C 9: 83 percent / H2; amberlit IR-45(OH(-)) / Pd/C / methanol / 5171.48 Torr 10: 85 percent / triethylamine tris(hydrogen fluoride); Et3N / tetrahydrofuran / 0.5 h / 20 °C View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → C46H74N4O27P2Si*2C6H15N

Conditions

Yield

Multi-step reaction with 9 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C 4: 82 percent / N-iodosuccinimide; AgOTf / CH2Cl2 / 0.5 h / -20 °C 5: 97 percent / imidazole; PCl3 / acetonitrile / 0.17 h / 20 °C 6: pivaloyl chloride; pyridine / 2 h 7: 351 mg / aq. I2; pyridine / -40 - -10 °C 8: NiCl2(H2O)6; NaBH4 / methanol / 0 °C View Scheme

1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside (68733-20-0) → 2-aminoethyl-(2-acetamido-3,4-di-O-acetyl-6-O-(tert-butyldimethylsilyl)-2-deoxy-α-D-mannopyranosyl phosphate)-(1,6)-(2-acetamido-3,4-di-O-acetyl-2-deoxy-α-D-mannopyranosyl phosphate)-(1,6)-(2-acetamido-3,4-di-O-acetyl-2-deoxy-α-D-mannopyranoside) bis-triethylammonium salt

Conditions

Yield

Multi-step reaction with 11 steps 1: 68 percent / 4 Angstroem molecular sieves; BF3*OEt2 / CH2Cl2 / 7 h 2: NaOMe / methanol / 1 h 3: pyridine / 20 °C 4: 82 percent / N-iodosuccinimide; AgOTf / CH2Cl2 / 0.5 h / -20 °C 5: 97 percent / imidazole; PCl3 / acetonitrile / 0.17 h / 20 °C 6: pivaloyl chloride; pyridine / 2 h 7: 351 mg / aq. I2; pyridine / -40 - -10 °C 8: NiCl2(H2O)6; NaBH4 / methanol / 0 °C 9: 83 percent / H2; amberlit IR-45(OH(-)) / Pd/C / methanol / 5171.48 Torr View Scheme

Upstream product

• 1600-27-7 mercury(II) diacetate 
• 2873-29-2 D-glucal triacetate 
• 127-09-3 sodium acetate 
• 668481-16-1 Acetic acid (2R,3S,4R)-4-acetoxy-2-acetoxymethyl-5-azido-6-nitrooxy-tetrahydro-pyran-3-yl ester 
• 129217-24-9 4,6-O-benzylidene-1-O-methyl-2-O-trifluoromethylsulfonate-α-D-glucopyranoside 
• 108-24-7 acetic anhydride 
• 116003-78-2 Methyl 2-azido-2-deoxy-4,6-O-(phenylmethylene)-α-D-mannopyranoside 
• 3162-96-7 4,6-O-benzylidene-1-O-methyl-α-D-glucopyranoside 
• 4710-95-6 D-mannosamine hydrochloride 
• 97-30-3 methyl-alpha-D-glucopyranoside 
• 3162-96-7 methyl 4,6-O-benzylidene-α-D-glucopyranoside 
• 4692-12-0 1,3,4,6-tetra-O-acetyl glucopyranose 
• 113544-40-4 1,3,4,6-tetra-O-acetyl-2-O-trifluoromethanesulfonyl-α-D-glucopyranose 
• 115945-97-6 methyl 3-O-acetyl-2-azido-4,6-O-benzylidene-2-deoxy-α-D-mannopyranoside 

Downstream Products

• 570412-04-3 4-nitrophenyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-mannopyranoside 
• 765308-75-6 p-methylphenyl 2-deoxy-2-azido-3,4,6-tri-O-acetyl-1-thio-D-mannopyranoside 
• 14040-20-1 Benzyl-2-acetamido-3-O-benzyl-4,6-O-benzyliden-2-desoxy-α-D-mannopyranosid 
• 95451-80-2 Benzyl-3,4,6-tri-O-acetyl-2-azido-2-desoxy-α-D-mannopyranosid 
• 95530-21-5 (Benzyl-2-<(benzyloxycarbonyl)amino>-2-desoxy-α-D-mannopyranosid)uronsaeure 
• 97604-79-0 Methyl-2-azido-3,4-di-O-benzyl-2-desoxy-β-D-mannopyranosid 
• 3554-91-4 benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-α-D-mannopyranoside 
• 95451-82-4 (Benzyl-2-azido-2-desoxy-α-D-mannopyranosid)uronsaeure 
• 95451-81-3 Benzyl-2-azido-2-desoxy-α-D-mannoopyranosid 
• 95451-85-7 (Benzyl-2-acetamido-3-O-benzyl-2-desoxy-α-D-mannopyranosid)uronsaeure 
• 42890-09-5 Benzyl-2-<(benzyloxycarbonyl)amino>-2-desoxy-α-D-mannopyranosid 
• 10380-86-6 phenylmethyl 2-acetylamino-2-deoxy-α-D-mannopyranoside 
• 35812-81-8 Benzyl-2-amino-2-desoxy-α-D-mannopyranosid 
• 97783-74-9 1,6-Anhydro-2-azido-3-O-benzyl-2-desoxy-4-O-(3,4,6-tri-O-acetyl-2-azido-2-desoxy-β-D-mannopyranosyl)-β-D-glucopyranose 

Relevant articles and documents

Improved synthesis of 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D- mannopyranose

By improved (anhydrous) work-up conditions of a triflate displacement reaction, the yield in the preparation of the versatile synthetic intermediate 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranose has been significantly enhanced. This important precursor is now available in three efficient steps from D-glucose.

Synthesis of 2-azido-2-deoxy- and 2-acetamido-2-deoxy-D-manno derivatives as versatile building blocks

Reported herein is the synthesis of a number of building blocks of 2-amino-2-deoxy-D-mannose from common D-glucose precursors.

Cu-free Sonogashira Type Cross-Coupling of 6-Halo-2-cyclopropyl-3-(pyridyl-3-ylmethyl) Quinazolin-4(3H)-ones as Potential Antimicrobial Agents

C(sp)–C(sp2) bond formation via Sonogashira cross-coupling reactions on 6-halo-2-cyclopropyl-3-(pyridyl-3-ylmethyl)quinazolin-4(3H)-ones with appropriate alkynes was explored. Optimization of reaction conditions with various catalysts, ligands, bases, and solvents was conducted. The combination of PdCl2(MeCN)2 with X-Phos proved to be the best metal–ligand system for this conversion in the presence of triethylamine (Et3N) in tetrahydrofuran at room temperature for iodosubstrates, at 80°C for the bromosubstrates in 8?h, and also for the chlorosubstrates in 16?h. We also demonstrated synthesis of a successful diversity-oriented synthesis library of highly functionalized quinazolinones via Cu-free Sonogashira coupling of diverse aryl halides and azido-alkyne (“click”) ligation reactions with substituted azides. The library exhibited significant antimicrobial activity when screened against several microorganisms.