14168-65-1

Basic information

• Product Name: 1,6-ANHYDRO-BETA-D-MANNOPYRANOSE
• Synonyms: MANNOSAN;1,6-ANHYDRO-BETA-D-MANNOPYRANOSE;1,6-ANHYDRO-B-D-MANNOPYRANOSE;Anhydro-beta-D-mannopyranose;.beta.-D-Mannopyranose, 1,6-anhydro-;1,6-ANHYDRO-BETA-MANNOPYRANOSE 99%;1,6-Anhydro--D-mannopyranose;1,6-Anhydro-D-mannose
• CAS NO: 14168-65-1
• Molecular Formula: C₆H₁₀O₅
• Molecular Weight: 162.14
• EINECS: 207-855-0
• Product Categories: Carbohydrates & Derivatives
• Mol File: 14168-65-1.mol
• Article Data: 21

Chemical Properties

• Melting Point: 182-184
• Boiling Point: 383.754 °C at 760 mmHg
• Flash Point: 185.888 °C
• Appearance: White crystalline solid
• Density: 1.689 g/cm³
• Vapor Pressure: 0mmHg at 25°C
• Refractive Index: 1.62
• Storage Temp.: 2-8°C
• Solubility: DMSO (Slightly), Methanol (Slightly), Water (Slightly, Sonicated)
• CAS DataBase Reference: 1,6-ANHYDRO-BETA-D-MANNOPYRANOSE(CAS DataBase Reference)
• NIST Chemistry Reference: 1,6-ANHYDRO-BETA-D-MANNOPYRANOSE(14168-65-1)
• EPA Substance Registry System: 1,6-ANHYDRO-BETA-D-MANNOPYRANOSE(14168-65-1)

Safety Data

• Hazard Codes: Xi,Xn
• Statements: 20/21/22-36/37/38
• Safety Statements: 26-36
• Hazardous Substances Data: 14168-65-1(Hazardous Substances Data)

Usage

Description

1,6-Anhydro-β-D-mannopyranose is a major organic tracer generated by burned cellulose. This compound is one of several that are used to evaluate, in atmospheric samples, the burning of wood.

Chemical Properties

White Crystalline Solid

Uses

Different sources of media describe the Uses of 14168-65-1 differently. You can refer to the following data:
1. An anhydro sugar with gustatory properties.
2. Monosaccharide anhydrides, new markers of toasted oak wood used for ageing wines and distillates.
3. 1,6-ANHYDRO-BETA-D-MANNOPYRANOSE is a major organic tracer generated by burned cellulose. This compound is one of several that are used to evaluate, in atmospheric samples, the burning of wood.

InChI:InChI=1/C6H10O5/c7-3-2-1-10-6(11-2)5(9)4(3)8/h2-9H,1H2/t2-,3+,4-,5-,6+/m0/s1

Synthetic route

D-Mannose (530-26-7) → mannosan (14168-65-1)

Conditions	Yield
With p-toluenesulfonyl chloride In pyridine for 4h; Ambient temperature;	80%
With pyridine; p-toluenesulfonyl chloride at 20℃; for 21h; Inert atmosphere;	48.4%
With toluene-4-sulfonic acid In N,N-dimethyl-formamide	20%

6-O-p-toluenesulfonyl-D-mannopyranose (6619-07-4, 26391-80-0, 121363-57-3, 121363-64-2, 121363-65-3, 121363-70-0) → mannosan (14168-65-1)

Conditions	Yield
NaOH In pyridine; sodium hydroxide for 1h; Ambient temperature;	77%
With 1,8-diazabicyclo[5.4.0]undec-7-ene In ethanol Ambient temperature;
With sodium hydride In N,N-dimethyl-formamide for 15h; Ambient temperature;
With 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile for 0.5h; Ambient temperature;

1,6-anhydro-2,3,4-tri-O-benzyl-β-D-mannopyranose (20888-02-2) → 1,6-anhydro-3-O-benzoyl-β-D-mannopyranose (104477-48-7) + mannosan (14168-65-1)

Conditions	Yield
palladium on activated charcoal In isopropyl alcohol for 4h; Heating;	A 40% B n/a
With isopropyl alcohol; palladium on activated charcoal for 4h; Heating;	A 40% B n/a

2,3,4-tri-O-acetyl-1,6-anhydro-β-D-mannopyranose (13242-48-3) → mannosan (14168-65-1)

Conditions	Yield
With methanol; barium methoxide

D-Mannose (3458-28-4) → mannosan (14168-65-1)

Conditions	Yield
With toluene-4-sulfonic acid; benzene In N,N-dimethyl-formamide

(1R,2S,6S,7R,8R)-7-Allyloxy-4-vinyl-3,5,10,11-tetraoxa-tricyclo[6.2.1.02,6]undecane (102794-49-0) → mannosan (14168-65-1)

Conditions	Yield
With sodium acetate; palladium dichloride In acetic acid at 20℃; for 24h;

1,6-anhydro-2,3-O-isopropylidene-β-D-mannopyranose (14440-51-8) → mannosan (14168-65-1)

Conditions	Yield
With pyridinium p-toluenesulfonate In methanol for 30h; Heating;

sulfuric acid (7664-93-9) + 1,6:3,4-dianhydro-β-D-altropyranose (3868-04-0) → mannosan (14168-65-1)

O2,O3-isopropyliden-1,6-anhydro-β-D-mannopyranose → mannosan (14168-65-1)

Conditions	Yield
With sulfuric acid

D-Mannose (3458-28-4) + aqueous sulfuric acid (0.2n) → mannosan (14168-65-1)

D-Mannose (530-26-7) + p-toluenesulfonyl chloride (98-59-9) → mannosan (14168-65-1)

Conditions	Yield
Stage #1: D-Mannose; p-toluenesulfonyl chloride Tosylation; Stage #2: With sodium hydroxide In water Cyclization; Further stages.;

dianhydroaltrose (71856-30-9) → mannosan (14168-65-1)

Conditions	Yield
Stage #1: dianhydroaltrose With boron trifluoride diethyl etherate Stage #2: With sodium methylate In methanol

1,6-anhydro-2-O-benzoyl-β-D-mannopyranoside → mannosan (14168-65-1)

Conditions	Yield
With sodium methylate In methanol

1,6-anhydro-2,3,4-tri-O-benzoyl-β-D-mannopyranose (5334-19-0) → mannosan (14168-65-1)

Conditions	Yield
With sodium methylate In methanol

2,3-isopropylidenedioxy-D-mannono-γ-lactone (126354-67-4) → mannosan (14168-65-1)

Conditions	Yield
Multi-step reaction with 5 steps 1: 61 percent / pyridine / 10 h / Ambient temperature 2: 98 percent / imidazole / dimethylformamide / 10 h / Ambient temperature 3: 90 percent / iBu2AlH / hexane; toluene / 4 h / -78 °C 4: 12 percent / NaH / dimethylformamide / 1.5 h / Ambient temperature 5: pyridinium p-toluenesulfonate / methanol / 30 h / Heating View Scheme
Multi-step reaction with 6 steps 1: 61 percent / pyridine / 10 h / Ambient temperature 2: 98 percent / imidazole / dimethylformamide / 10 h / Ambient temperature 3: 90 percent / iBu2AlH / hexane; toluene / 4 h / -78 °C 4: 35 percent / NaH / dimethylformamide / 1.5 h / Ambient temperature 5: 70 percent / Bu4NF / tetrahydrofuran / 0.17 h 6: pyridinium p-toluenesulfonate / methanol / 30 h / Heating View Scheme

2,3-O-Isopropylidene-4-O-t-butyldimethylsilyl-1,6-anhydro-β-D-mannopyranose (150161-01-6) → mannosan (14168-65-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: 70 percent / Bu4NF / tetrahydrofuran / 0.17 h 2: pyridinium p-toluenesulfonate / methanol / 30 h / Heating View Scheme

2,3-O-Isopropylidene-6-O-(p-tolylsulfonyl)-D-mannono-1,4-lactone (150160-98-8) → mannosan (14168-65-1)

Conditions	Yield
Multi-step reaction with 4 steps 1: 98 percent / imidazole / dimethylformamide / 10 h / Ambient temperature 2: 90 percent / iBu2AlH / hexane; toluene / 4 h / -78 °C 3: 12 percent / NaH / dimethylformamide / 1.5 h / Ambient temperature 4: pyridinium p-toluenesulfonate / methanol / 30 h / Heating View Scheme
Multi-step reaction with 5 steps 1: 98 percent / imidazole / dimethylformamide / 10 h / Ambient temperature 2: 90 percent / iBu2AlH / hexane; toluene / 4 h / -78 °C 3: 35 percent / NaH / dimethylformamide / 1.5 h / Ambient temperature 4: 70 percent / Bu4NF / tetrahydrofuran / 0.17 h 5: pyridinium p-toluenesulfonate / methanol / 30 h / Heating View Scheme

2,3-O-Isopropylidene-5-O-tert-butyldimethylsilyl-6-O-(p-tolylsulfonyl)-D-mannofuranose → mannosan (14168-65-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: 12 percent / NaH / dimethylformamide / 1.5 h / Ambient temperature 2: pyridinium p-toluenesulfonate / methanol / 30 h / Heating View Scheme
Multi-step reaction with 3 steps 1: 35 percent / NaH / dimethylformamide / 1.5 h / Ambient temperature 2: 70 percent / Bu4NF / tetrahydrofuran / 0.17 h 3: pyridinium p-toluenesulfonate / methanol / 30 h / Heating View Scheme

2,3-O-Isopropylidene-5-O-tert-butyldimethylsilyl-6-O-(p-tolylsulfonyl)-D-mannono-1,4-lactone (150160-99-9) → mannosan (14168-65-1)

Conditions	Yield
Multi-step reaction with 3 steps 1: 90 percent / iBu2AlH / hexane; toluene / 4 h / -78 °C 2: 12 percent / NaH / dimethylformamide / 1.5 h / Ambient temperature 3: pyridinium p-toluenesulfonate / methanol / 30 h / Heating View Scheme
Multi-step reaction with 4 steps 1: 90 percent / iBu2AlH / hexane; toluene / 4 h / -78 °C 2: 35 percent / NaH / dimethylformamide / 1.5 h / Ambient temperature 3: 70 percent / Bu4NF / tetrahydrofuran / 0.17 h 4: pyridinium p-toluenesulfonate / methanol / 30 h / Heating View Scheme

2,3:5,6-di-O-isopropylidene-α-D-mannofuranose (14131-84-1) → mannosan (14168-65-1)

Conditions	Yield
Multi-step reaction with 7 steps 1: 80 percent / Collins' reagent / CH2Cl2 / 0.5 h / Ambient temperature 2: gl. AcOH, water / 4 h / 60 °C 3: 61 percent / pyridine / 10 h / Ambient temperature 4: 98 percent / imidazole / dimethylformamide / 10 h / Ambient temperature 5: 90 percent / iBu2AlH / hexane; toluene / 4 h / -78 °C 6: 12 percent / NaH / dimethylformamide / 1.5 h / Ambient temperature 7: pyridinium p-toluenesulfonate / methanol / 30 h / Heating View Scheme
Multi-step reaction with 8 steps 1: 80 percent / Collins' reagent / CH2Cl2 / 0.5 h / Ambient temperature 2: gl. AcOH, water / 4 h / 60 °C 3: 61 percent / pyridine / 10 h / Ambient temperature 4: 98 percent / imidazole / dimethylformamide / 10 h / Ambient temperature 5: 90 percent / iBu2AlH / hexane; toluene / 4 h / -78 °C 6: 35 percent / NaH / dimethylformamide / 1.5 h / Ambient temperature 7: 70 percent / Bu4NF / tetrahydrofuran / 0.17 h 8: pyridinium p-toluenesulfonate / methanol / 30 h / Heating View Scheme

2,3,5,6-di-O-isopropylidene-D-mannono-1,4-lactone (7306-64-1, 14440-56-3, 23262-80-8, 27108-15-2, 49561-21-9, 67642-42-6) → mannosan (14168-65-1)

Conditions	Yield
Multi-step reaction with 6 steps 1: gl. AcOH, water / 4 h / 60 °C 2: 61 percent / pyridine / 10 h / Ambient temperature 3: 98 percent / imidazole / dimethylformamide / 10 h / Ambient temperature 4: 90 percent / iBu2AlH / hexane; toluene / 4 h / -78 °C 5: 12 percent / NaH / dimethylformamide / 1.5 h / Ambient temperature 6: pyridinium p-toluenesulfonate / methanol / 30 h / Heating View Scheme
Multi-step reaction with 7 steps 1: gl. AcOH, water / 4 h / 60 °C 2: 61 percent / pyridine / 10 h / Ambient temperature 3: 98 percent / imidazole / dimethylformamide / 10 h / Ambient temperature 4: 90 percent / iBu2AlH / hexane; toluene / 4 h / -78 °C 5: 35 percent / NaH / dimethylformamide / 1.5 h / Ambient temperature 6: 70 percent / Bu4NF / tetrahydrofuran / 0.17 h 7: pyridinium p-toluenesulfonate / methanol / 30 h / Heating View Scheme

D-Mannose (3458-28-4) → 1,6-Anhydro-β-D-mannohexofuranose (31880-33-8) + mannosan (14168-65-1)

Conditions	Yield
With water In sulfolane at 220℃; for 0.05h; Microwave irradiation;	A 14.7 %Chromat. B 63.9 %Chromat.

methyl α-D-mannofuranoside (4097-91-0) → 1,6-Anhydro-β-D-mannohexofuranose (31880-33-8) + mannosan (14168-65-1)

Conditions	Yield
In sulfolane at 240℃; for 0.05h; Microwave irradiation;	A 57.1 %Chromat. B 5.8 %Chromat.
With water In sulfolane at 240℃; for 0.05h; Microwave irradiation;	A 12.5 %Chromat. B 48.1 %Chromat.

(2R,3S,4S,5S,6S)-2-(hydroxymethyl)-6-methoxytetrahydro-2H-pyran-3,4,5-triol (617-04-9) → mannosan (14168-65-1)

Conditions	Yield
With water In sulfolane at 280℃; for 0.05h; Microwave irradiation;	79.8 %Chromat.

6-O-toluenesulfonyl-β-D-mannopyranose → mannosan (14168-65-1)

Conditions	Yield
With sodium hydroxide at 0 - 20℃; Inert atmosphere;

β-D-mannose (7322-31-8) → mannosan (14168-65-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: pyridine / 1 h / 0 - 20 °C / Inert atmosphere 2: sodium hydroxide / 0 - 20 °C / Inert atmosphere View Scheme

acetic anhydride (108-24-7) + mannosan (14168-65-1) → D-Mannose pentaacetate (83-87-4, 604-68-2, 604-69-3, 2152-77-4, 4026-35-1, 4163-59-1, 4163-60-4, 4163-61-5, 4163-65-9, 4257-94-7, 4257-96-9, 16299-15-3, 19186-39-1, 19189-55-0, 25878-60-8, 25941-03-1, 32445-48-0, 32445-49-1, 32445-53-7, 32445-54-8, 34685-58-0, 34685-59-1, 43168-42-9, 43168-44-1, 43169-22-8, 43169-25-1, 66966-07-2, 70749-17-6, 80184-01-6, 93221-01-3, 93221-02-4, 99630-88-3, 109215-53-4, 115792-70-6, 115792-73-9, 139894-92-1, 139973-25-4, 144071-49-8, 147648-81-5)

Conditions	Yield
scandium tris(trifluoromethanesulfonate) at 20℃; for 5h;	95%

benzyl bromide (100-39-0) + mannosan (14168-65-1) → 1,6-anhydro-2,3,4-tri-O-benzyl-β-D-mannopyranose (20888-02-2)

Conditions	Yield
Stage #1: mannosan With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃; for 1h; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 15 - 20℃; for 15h;	92%
With barium dihydroxide; barium(II) oxide In N,N-dimethyl-formamide for 1h; Ambient temperature; Yield given;
With tetra-(n-butyl)ammonium iodide; sodium hydride 1.) DMF, DMF; Multistep reaction;

triisopropylsilyl trifluoromethanesulfonate (80522-42-5) + mannosan (14168-65-1) → 1,6-anhydro-2,3,4-tris-O-(triisopropylsilyl)-β-D-mannopyranose (388578-36-7)

Conditions	Yield
With pyridine In 1,1,2,2-tetrachloroethane at 110℃; for 15h;	92%

tert-butyldimethylsilane (29681-57-0) + mannosan (14168-65-1) → 2,4-O-bis(t-butyldimethylsilyl)-1,6-anhydro-β-D-mannose + 2,3,4-tris(t-butyldimethylsilyl)-1,6-anhydro-β-D-mannose

Conditions	Yield
With [Ir(COD)(PPh3)2]SbF6 In N,N-dimethyl acetamide at 70℃;	A 86% B 5%

chloro-trimethyl-silane (75-77-4) + mannosan (14168-65-1) → 1,6-anhydro-2,3,4-tris-O-trimethylsilyl-β-D-mannopyranose

Conditions	Yield
With triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;	86%

triisopropylsilyl trifluoromethanesulfonate (80522-42-5) + mannosan (14168-65-1) → 1,6-anhydro-2,4-bis-O-(triisopropylsilyl)-β-D-mannopyranose (481704-39-6)

Conditions	Yield
In pyridine; dichloromethane	80%

benzoyl chloride (98-88-4) + mannosan (14168-65-1) → 1,6-anhydro-2-O-benzoyl-β-D-mannopyranoside

Conditions	Yield
With iron(III)-acetylacetonate; N-ethyl-N,N-diisopropylamine In acetonitrile at 20℃; for 4h; Green chemistry; regioselective reaction;	78%

9,9-dichloro-9H-fluorene (25023-01-2) + mannosan (14168-65-1) → 1,6-anhydro-2,3-O-fluoren-9-ylidene-β-D-mannopyranose (137016-99-0)

Conditions	Yield
With pyridine at 110℃; for 96h;	73%

benzyl bromide (100-39-0) + mannosan (14168-65-1) → 1,6-anhydro-2-O-benzyl-β-D-mannopyranoside (116730-88-2)

Conditions	Yield
With diphenylborate ethanolamine ester; silver(l) oxide In acetonitrile at 40℃; for 48h; Inert atmosphere; regioselective reaction;	73%

1-bromomethyl-4-bromobenzene (589-15-1) + mannosan (14168-65-1) → 1,6-anhydro-2-O-(4-bromobenzyl)-β-D-mannopyranoside (1309382-38-4) + 1,6-anhydro-3-O-(4-bromobenzyl)-β-D-mannopyranoside

Conditions	Yield
With diphenylborate ethanolamine ester; silver(l) oxide In acetonitrile at 40℃; for 48h; Inert atmosphere; regioselective reaction;	A 73% B n/a

2-bromomethylnaphthyl bromide (939-26-4) + mannosan (14168-65-1) → 1,6-anhydro-2-O-(2-naphthyl)methyl-β-D-mannopyranoside (1309382-40-8)

Conditions	Yield
With diphenylborate ethanolamine ester; silver(l) oxide In acetonitrile at 40℃; for 48h; Inert atmosphere; regioselective reaction;	71%

acrylic acid methyl ester (292638-85-8) + mannosan (14168-65-1) → (1R,2R,3S,4S,5R)-2,4-dihydroxydihydro-5'H-6,8-dioxaspiro[bicyclo[3.2.1]octane-3,2'-furan]-5'-one

Conditions	Yield
With Quinuclidine; [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate; oxybis(diphenylborane) In acetonitrile at 25℃; for 16h; Reagent/catalyst; Irradiation; Inert atmosphere; Schlenk technique; Sealed tube;	68%

benzaldehyde dimethyl acetal (1125-88-8) + mannosan (14168-65-1) → 1,6-anhydro-2,3-O-endo-benzylidene-β-D-mannopyranose (71049-45-1)

Conditions	Yield
With toluene-4-sulfonic acid In N,N-dimethyl-formamide at 50℃; for 1h;	65.2%

benzyl bromide (100-39-0) + mannosan (14168-65-1) → 1,6-anhydro-3-O-benzyl-β-D-mannopyranose (116429-52-8) + 1,6-anhydro-2-O-benzyl-β-D-mannopyranoside (116730-88-2)

Conditions	Yield
With 3 A molecular sieve; bis(tri-n-butyltin)oxide; 1-methyl-1H-imidazole; tetra-(n-butyl)ammonium iodide In toluene 1.) reflux, 15 h; 2.) 2 h;	A 25% B 65%
With 3 A molecular sieve; bis(tri-n-butyltin)oxide; 1-methyl-1H-imidazole; tetrabutylammomium bromide In toluene 1.) reflux, 15 h; 2.) 8 h;	A 38% B 52%

1,2-propylene cyclic carbonate (108-32-7) + mannosan (14168-65-1) → poly(1,6-anhydro-β-D-mannopyranose-co-propylene carbonate)

Conditions	Yield
With 3-methyl-2-butynyltetramethylenesulfonium hexafluoroantimonate at 90℃; for 0.333333h;	64%

mannosan (14168-65-1) → polymer, product of cationic polymerization, branching degree 0.44, Mw 1.050E4, PDI 1.43 by SEC, Mw 6.37E5 by SLS; monomer(s): 1,6-anhydro-β-D-mannopyranose

Conditions	Yield
With 1-(2-butenyl)tetrahydrothiophenium hexafluoroantimonate In various solvent(s) at 150℃; for 0.666667h;	63%

Benzyloxymethyl chloride (3587-60-8) + mannosan (14168-65-1) → 1,6-anhydro-2-O-benzyloxymethyl-β-D-mannopyranoside (1309382-41-9) + 1,6-anhydro-3-O-benzyloxymethyl-β-D-mannopyranoside

Conditions	Yield
With diphenylborate ethanolamine ester; silver(l) oxide In acetonitrile at 40℃; for 48h; Inert atmosphere; regioselective reaction;	A 63% B n/a

mannosan (14168-65-1) → polymer, product of cationic polymerization, branching degree 0.43, Mw 3.20E3, PDI 1.35 by SEC, Mw 8.05E4 by SLS; monomer(s): 1,6-anhydro-β-D-mannopyranose

Conditions	Yield
With 1-(2-butenyl)tetrahydrothiophenium hexafluoroantimonate In various solvent(s) at 130℃; for 0.333333h;	61.6%

mannosan (14168-65-1) → polymer, product of cationic polymerization, branching degree 0.43, Mw 4.30E3, PDI 1.49 by SEC, Mw 9.63E4 by SLS; monomer(s): 1,6-anhydro-β-D-mannopyranose

Conditions	Yield
With 1-(2-butenyl)tetrahydrothiophenium hexafluoroantimonate In various solvent(s) at 150℃; for 0.333333h;	61.1%

mannosan (14168-65-1) → polymer, product of cationic polymerization, branching degree 0.41, Mw 2.48E3, PDI 1.31 by SEC, Mw 6.94E4 by SLS; monomer(s): 1,6-anhydro-β-D-mannopyranose

Conditions	Yield
With 1-(2-butenyl)tetrahydrothiophenium hexafluoroantimonate In various solvent(s) at 130℃; for 0.666667h;	57%

mannosan (14168-65-1) → polymer, product of cationic polymerization, branching degree 0.42, Mw 2.17E3, PDI 1.30 by SEC, Mw 3.42E4 by SLS; monomer(s): 1,6-anhydro-β-D-mannopyranose

Conditions	Yield
With 1-(2-butenyl)tetrahydrothiophenium hexafluoroantimonate In various solvent(s) at 130℃; for 0.333333h;	56.6%

2-(dimethoxymethyl)naphthalene (77196-31-7) + mannosan (14168-65-1) → endo-1,6-anhydro-2,3-O-(2-naphthyl)methylene-β-D-mannopyranose (502690-08-6) + exo-1,6-anhydro-2,3-O-(2-naphthyl)methylene-β-D-mannopyranose

Conditions	Yield
With toluene-4-sulfonic acid In N,N-dimethyl-formamide at 20℃; for 24h;	A 55% B 9.2%

N-benzoyloxybenzotriazole (54769-36-7) + mannosan (14168-65-1) → 1,6-anhydro-2-O-benzoyl-β-D-mannopyranoside + 1,6-anhydro-2,4-di-O-benzoyl-β-D-mannopyranose (676342-64-6) + 1,6-anhydro-2,3,4-tri-O-benzoyl-β-D-mannopyranose (5334-19-0)

Conditions	Yield
With pyridine at 20℃; for 76h;	A 15% B 54% C 26%

N-benzoyloxybenzotriazole (54769-36-7) + mannosan (14168-65-1) → 1,6-anhydro-2,4-di-O-benzoyl-β-D-mannopyranose (676342-64-6)

Conditions	Yield
With pyridine	54%

benzaldehyde dimethyl acetal (1125-88-8) + mannosan (14168-65-1) → 1,6-anhydro-2,3-O-endo-benzylidene-β-mannopyranose (5349-10-0)

Conditions	Yield
With toluene-4-sulfonic acid In N,N-dimethyl-formamide at 50℃; under 30 Torr; for 3h;	38%
With toluene-4-sulfonic acid In N,N-dimethyl-formamide at 65 - 75℃; for 3h;	24%

p-Anisaldehyde dimethyl acetal (2186-92-7) + mannosan (14168-65-1) → 1,6-anhydro-endo-2,3-O-(4-methoxybenzylidene)-β-D-mannopyranose + 1,6-Anhydro-endo-2,3-O-(4-methoxybenzylidene)-β-D-mannopyranose (93793-97-6)

Conditions	Yield
With toluene-4-sulfonic acid In N,N-dimethyl-formamide at 50℃; under 225.023 Torr; for 4h; optical yield given as %de;	A n/a B 31%
With toluene-4-sulfonic acid In N,N-dimethyl-formamide

mannosan (14168-65-1) → polymer, product of cationic polymerization, branching degree 0.44, Mw 5.84E3, PDI 1.84 by SEC, Mw 8.09E4 by SLS; monomer(s): 1,6-anhydro-β-D-mannopyranose

Conditions	Yield
With 1-(2-butenyl)tetrahydrothiophenium hexafluoroantimonate at 210℃; for 0.0166667h;	23.8%

Upstream product

• 3458-28-4 D-Mannose 
• 7664-93-9 sulfuric acid 
• 3868-04-0 1,6:3,4-dianhydro-β-D-altropyranose 
• 7322-31-8 β-D-mannose 
• 617-04-9 (2R,3S,4S,5S,6S)-2-(hydroxymethyl)-6-methoxytetrahydro-2H-pyran-3,4,5-triol 
• 4097-91-0 methyl α-D-mannofuranoside 
• 7306-64-1 2,3,5,6-di-O-isopropylidene-D-mannono-1,4-lactone 
• 14131-84-1 2,3:5,6-di-O-isopropylidene-α-D-mannofuranose 
• 150160-99-9 2,3-O-Isopropylidene-5-O-tert-butyldimethylsilyl-6-O-(p-tolylsulfonyl)-D-mannono-1,4-lactone 
• 150160-98-8 2,3-O-Isopropylidene-6-O-(p-tolylsulfonyl)-D-mannono-1,4-lactone 
• 150161-01-6 2,3-O-Isopropylidene-4-O-t-butyldimethylsilyl-1,6-anhydro-β-D-mannopyranose 
• 126354-67-4 2,3-isopropylidenedioxy-D-mannono-γ-lactone 
• 5334-19-0 1,6-anhydro-2,3,4-tri-O-benzoyl-β-D-mannopyranose 
• 71856-30-9 dianhydroaltrose 

Downstream Products

• 17073-95-9 1,6-anhydro-3,4-isopropylidene-D-galactopyranose 
• 76752-93-7 1,6-anhydro-2-O-benzoyl-3-desoxy-β-D-arabino-hexopyranose 
• 71019-71-1 1,6-anhydro-2-O-benzoyl-3-bromo-3-desoxy-β-D-altopyranose 
• 55682-57-0 1,6-anhydro-2-azido-3-O-benzyl-2-deoxy-β-D-glucopyranose 
• 33208-48-9 1,6-anhydro-2,4-di-O-benzyl-β-D-glucopyranose 
• 97292-00-7 1,6-Anhydro-2-O-(p-toluenesulphonyl)-β-D-mannopyranose 
• 50880-93-8 tris-O-(toluene-4-sulfonyl)-1,6-anhydro-β-D-mannopyranose 
• 5334-19-0 1,6-anhydro-2,3,4-tri-O-benzoyl-β-D-mannopyranose 
• 13242-48-3 2,3,4-tri-O-acetyl-1,6-anhydro-β-D-mannopyranose 
• 71049-45-1 1,6-anhydro-2,3-O-endo-benzylidene-β-D-mannopyranose 
• 14440-51-8 1,6-anhydro-2,3-O-isopropylidene-β-D-mannopyranose 
• 19879-84-6 2,3,4,6-tetra-O-acetyl-1-thio-α-D-mannopyranoside 
• 17371-38-9 C₆H₈O₅ 

Relevant articles and documents

Selective synthesis of 1,6-anhydro-β-D-mannopyranose and -mannofuranose using microwave-assisted heating

The dehydration of D-mannose and the demethanolization of methyl-α-D-mannopyranoside (MαMP) or methyl-α-D- mannofuranoside (MαMF) were examined using microwave-assisted heating for a 3-min irradiation at temperature from 120 to 280 °C in ordinary or dry sulfolane without any catalyst. The microwave-assisted heating of MαMP and MαMF smoothly proceeded to selectively afford the anhydromannoses, 1,6-anhydro-β-D-mannopyranose (AMP) and 1,6-anhydro-β-D-mannofuranose (AMF), respectively, in high yields. For MαMP in ordinary sulfolane at 240 °C, AMP was selectively obtained in the AMF:AMP ratio of 4:96, whereas AMF was the major product at the AMF:AMP ratio of 97:3 from MαMF in dry sulfolane at 220 °C.

A Unified Strategy to Access 2- And 4-Deoxygenated Sugars Enabled by Manganese-Promoted 1,2-Radical Migration

The selective manipulation of carbohydrate scaffolds is challenging due to the presence of multiple, nearly chemically indistinguishable O-H and C-H bonds. As a result, protecting-group-based synthetic strategies are typically necessary for carbohydrate modification. Here we report a concise semisynthetic strategy to access diverse 2- and 4-deoxygenated carbohydrates without relying on the exhaustive use of protecting groups to achieve site-selective reaction outcomes. Our approach leverages a Mn2+-promoted redox isomerization step, which proceeds via sugar radical intermediates accessed by neutral hydrogen atom abstraction under visible light-mediated photoredox conditions. The resulting deoxyketopyranosides feature chemically distinguishable functional groups and are readily transformed into diverse carbohydrate structures. To showcase the versatility of this method, we report expedient syntheses of the rare sugars l-ristosamine, l-olivose, l-mycarose, and l-digitoxose from commercial l-rhamnose. The findings presented here validate the potential for radical intermediates to facilitate the selective transformation of carbohydrates and showcase the step and efficiency advantages attendant to synthetic strategies that minimize a reliance upon protecting groups.

Synthesis of unstable 4-benzoyl-1,6-anhydro-3-keto-β-D-mannopyranose via stereoselective photobromination of 2,3-isopropylidene-4-benzoyl-1,6-anhydro-β-D-mannopyranose

Stereoselective photobromination of 1,6-anhydro-β-D-glucopyranose derivatives occurs at exo-H6. However, photobromination of 4-benzoyl-2,3-isopropylidene-1,6-anhydro-β-D-mannopyranose 6 produced unstable 4-benzoyl-1,6-anhydro-3-keto-β-D-mannopyranose 7. The mechanism of stereoselective oxidation at C-3 could be attributed to the facile radical proton abstraction at C-3, followed by the subsequent bromination of the isopropylidene group, which was subsequently eliminated during the aqueous workup. Thus, the aim of this article is to identify the molecular structure of the unstable compound 7.