109428-30-0

Basic information

• Product Name: 1,5:2,3-Dianhydro-4,6-O-benzylidene-D-allitol
• Synonyms: 1,5:2,3-Dianhydro-4,6-O-(phenylmethylene)-D-allitol;(1aS,3aR,7aR,7bS)-6-Phenylhexahydrooxireno[2',3':4,5]pyrano[3,2-d][1,3]dioxine
• CAS NO: 109428-30-0
• Molecular Formula: C₁₃H₁₄O₄
• Molecular Weight: 234.25
• Product Categories: Aromatics Compounds;Aromatics;Carbohydrates & Derivatives
• Mol File: 109428-30-0.mol

Chemical Properties

• Appearance: /
• Refractive Index: 1.552
• CAS DataBase Reference: 1,5:2,3-Dianhydro-4,6-O-benzylidene-D-allitol(CAS DataBase Reference)
• NIST Chemistry Reference: 1,5:2,3-Dianhydro-4,6-O-benzylidene-D-allitol(109428-30-0)
• EPA Substance Registry System: 1,5:2,3-Dianhydro-4,6-O-benzylidene-D-allitol(109428-30-0)

Safety Data

• Hazardous Substances Data: 109428-30-0(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
1,5:2,3-Dianhydro-4,6-O-benzylidene-D-allitol is used as a building block for the synthesis of protected D-Altritol nucleosides. These nucleosides are important components in the development of oligonucleotides, which have potential applications in gene therapy, antisense therapy, and the creation of artificial genes.
Additionally, the compound can be utilized in the synthesis of various pharmaceutical agents, taking advantage of its protected hydroxyl groups to facilitate selective reactions and improve the overall yield of the desired products.

InChI:InChI=1/C13H14O4/c1-2-4-8(5-3-1)13-15-6-9-11(17-13)12-10(16-12)7-14-9/h1-5,9-13H,6-7H2/t9?,10?,11-,12+,13?/m1/s1

Synthetic route

(4aR,8aS)-2-phenyl-4,4a,6,8a-tetrahydro-pyrano[3,2-d][1,3]dioxine → 1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0)

Conditions	Yield
Stage #1: (4aR,8aS)-2-phenyl-4,4a,6,8a-tetrahydro-pyrano[3,2-d][1,3]dioxine With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 1h; Stage #2: With dimethylsulfide for 0.166667h;	38%

4-Methyl-benzoic acid (4aR,7S,8R,8aR)-2-phenyl-8-(toluene-4-sulfonyloxy)-hexahydro-pyrano[3,2-d][1,3]dioxin-7-yl ester → 1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0)

Conditions	Yield
With sodium methylate In toluene at 50℃; Yield given;

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 1,5-anhydro-2-azido-4,6-O-benzylidene-2-deoxy-D-altritol (921772-44-3)

Conditions	Yield
With sodium azide; ammonium chloride In 2-methoxy-ethanol; water at 100℃; for 18h;	95%
With sodium azide; ammonium chloride In 2-methoxy-ethanol; water at 100℃; for 18h; Inert atmosphere;	95%

uracil (66-22-8) + 1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 1-((4aR,7R,8S,8aS)-8-hydroxy-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-7-yl)-1H-pyrimidine-2,4-dione (181711-37-5)

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 120℃;	69%
Stage #1: uracil With sodium hydride In DMF (N,N-dimethyl-formamide) for 1h; Heating / reflux; Stage #2: 1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol In DMF (N,N-dimethyl-formamide) for 24h; Heating / reflux;	29%

allylmagnesium bromide (2622-05-1) + 1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → (4aR,7R,8S,8aS)-7-allyl-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-8-ol

Conditions	Yield
Stage #1: allylmagnesium bromide With copper(l) iodide In tetrahydrofuran at -30℃; for 0.25h; Inert atmosphere; Stage #2: 1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol In tetrahydrofuran at -30℃; for 1.5h; Inert atmosphere; regioselective reaction;	69%
With copper(l) iodide In tetrahydrofuran at -30℃; for 1.5h; Inert atmosphere;	69%

adenine (66224-66-6, 66224-67-7, 66224-68-8, 66224-69-9, 134434-48-3, 134434-49-4, 134454-76-5, 134461-75-9) + 1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → (4aR,7R,8S,8aS)-7-(6-Amino-purin-9-yl)-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-8-ol (168696-01-3)

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 100℃;	54%

thymin (65-71-4) + 1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 1-((4aR,7R,8S,8aS)-8-hydroxy-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-7-yl)-5-methyl-1H-pyrimidine-2,4-dione

Conditions	Yield
Stage #1: thymin With sodium hydride In DMF (N,N-dimethyl-formamide) for 2h; Heating / reflux; Stage #2: 1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol In DMF (N,N-dimethyl-formamide) for 24h; Heating / reflux;	47%

2-azidoethanol (1517-05-1) + 1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → (4aR,7R,8S,8aS)-7-(2-azidoethoxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-8-ol

Conditions	Yield
Stage #1: 2-azidoethanol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.5h; Inert atmosphere; Stage #2: 1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol In N,N-dimethyl-formamide; mineral oil at 0 - 80℃; Inert atmosphere;	45%

5-iodouracil (696-07-1) + 1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 1-((4aR,7R,8S,8aS)-8-hydroxy-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-7-yl)-5-iodo-1H-pyrimidine-2,4-dione

Conditions	Yield
Stage #1: 5-iodouracil With sodium hydride In DMF (N,N-dimethyl-formamide) for 2h; Heating / reflux; Stage #2: 1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol In DMF (N,N-dimethyl-formamide) for 24h; Heating / reflux;	20%

6-chloropurine (87-42-3) + 1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → (4aR,7R,8S,8aS)-7-(6-Chloro-purin-9-yl)-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-8-ol

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 48h;	16%

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 1,5-anhydro-2-azido-2-deoxy-D-altritol (921772-45-4)

Conditions	Yield
Multi-step reaction with 2 steps 1: 95 percent / NaN3; NH4Cl / 2-methoxy-ethanol; H2O / 18 h / 100 °C 2: 66 percent / AcOH; water / 2 h / 95 °C View Scheme
Multi-step reaction with 2 steps 1: sodium azide; ammonium chloride / water; 2-methoxy-ethanol / 18 h / 100 °C / Inert atmosphere 2: acetic acid; water / 2 h / 95 °C View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 1,5-anhydro-2-azido-2-deoxy-6-O-phosphono-D-altritol diammonium salt

Conditions	Yield
Multi-step reaction with 3 steps 1.1: 95 percent / NaN3; NH4Cl / 2-methoxy-ethanol; H2O / 18 h / 100 °C 2.1: 66 percent / AcOH; water / 2 h / 95 °C 3.1: (MeO)3PO; POCl3 / 3 h / 0 °C 3.2: 46 percent / NH4OH; water / propan-2-ol View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 2-amino-1,5-anhydro-2-deoxy-6-O-phosphono-D-altritol sodium salt

Conditions	Yield
Multi-step reaction with 4 steps 1.1: 95 percent / NaN3; NH4Cl / 2-methoxy-ethanol; H2O / 18 h / 100 °C 2.1: 66 percent / AcOH; water / 2 h / 95 °C 3.1: (MeO)3PO; POCl3 / 3 h / 0 °C 3.2: 46 percent / NH4OH; water / propan-2-ol 4.1: H2; PtO2*H2O / H2O; methanol / 85 h / 20 °C / 1551.49 Torr 4.2: 91 percent / Dowex 50WX4-400 (Na+) / H2O View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 1,5-anhydro-2-(3-carbamoylpyridinium)-2-deoxy-6-O-phosphono-D-altritol (921772-48-7)

Conditions

Yield

Multi-step reaction with 5 steps 1.1: 95 percent / NaN3; NH4Cl / 2-methoxy-ethanol; H2O / 18 h / 100 °C 2.1: 66 percent / AcOH; water / 2 h / 95 °C 3.1: (MeO)3PO; POCl3 / 3 h / 0 °C 3.2: 46 percent / NH4OH; water / propan-2-ol 4.1: H2; PtO2*H2O / H2O; methanol / 85 h / 20 °C / 1551.49 Torr 4.2: 91 percent / Dowex 50WX4-400 (Na+) / H2O 5.1: 42 percent / Et3NH(+)HCO3(-) / methanol; H2O / 144 h / 40 °C View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → altritol nicotinamide adenine dinucleotide lithium salt

Conditions

Yield

Multi-step reaction with 6 steps 1.1: 95 percent / NaN3; NH4Cl / 2-methoxy-ethanol; H2O / 18 h / 100 °C 2.1: 66 percent / AcOH; water / 2 h / 95 °C 3.1: (MeO)3PO; POCl3 / 3 h / 0 °C 3.2: 46 percent / NH4OH; water / propan-2-ol 4.1: H2; PtO2*H2O / H2O; methanol / 85 h / 20 °C / 1551.49 Torr 4.2: 91 percent / Dowex 50WX4-400 (Na+) / H2O 5.1: 42 percent / Et3NH(+)HCO3(-) / methanol; H2O / 144 h / 40 °C 6.1: AgNO3 / formamide; pyridine / 65 h / 20 °C 6.2: 39 percent / LiOH View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 1,5-anhydro-3-O-benzoyl-2-deoxy-2-(uracil-1-yl)-D-altro-hexitol (215959-65-2)

Conditions	Yield
Multi-step reaction with 3 steps 3: 70 percent / aq. CF3CO2H / 1 h View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → Benzoic acid (4aR,7R,8S,8aS)-7-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-8-yl ester (215959-64-1)

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → N-[9-((4aR,7R,8S,8aS)-8-Hydroxy-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-7-yl)-9H-purin-6-yl]-benzamide

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 1,5-anhydro-3-O-benzoyl-2-deoxy-2-(N6-benzoyladenin-9-yl)-D-altro-hexitol (227079-12-1)

Conditions	Yield
Multi-step reaction with 4 steps 4: aq. CF3CO2H / 1 h View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → Benzoic acid (4aR,7R,8S,8aS)-7-(6-benzoylamino-purin-9-yl)-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-8-yl ester (227079-11-0)

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 1,5-anhydro-3-O-benzoyl-6-O-monomethoxytrityl-2-deoxy-2-(uracil-1-yl)-D-altro-hexitol (215959-66-3)

Conditions	Yield
Multi-step reaction with 4 steps 3: 70 percent / aq. CF3CO2H / 1 h 4: 74 percent / AgNO3, 2,4,6-collidine / dimethylformamide View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 1,5-anhydro-3-O-benzoyl-6-O-monomethoxytrityl-2-deoxy-2-(N6-benzoyladenin-9-yl)-D-altro-hexitol (227079-13-2)

Conditions	Yield
Multi-step reaction with 5 steps 4: aq. CF3CO2H / 1 h 5: AgNO3, 2,4,6-collidine / dimethylformamide View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 2-(Uracil-1-yl)-3-O-benzoyl-2-deoxy-4-O-[N,N-diisopropyl(2-cyanoethyl)]phosphoramidite-6-O-monomethoxytrityl-D-altritol

Conditions	Yield
Multi-step reaction with 5 steps 3: 70 percent / aq. CF3CO2H / 1 h 4: 74 percent / AgNO3, 2,4,6-collidine / dimethylformamide 5: 94 percent View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 2-(N6-Benzoyl-adenin-9-yl)-3-O-benzoyl-2-deoxy-4-O-[N,N-diisopropyl(2-cyanoethyl)]phosphoramidite-6-O-monomethoxytrityl-D-altritol

Conditions	Yield
Multi-step reaction with 6 steps 4: aq. CF3CO2H / 1 h 5: AgNO3, 2,4,6-collidine / dimethylformamide View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 4-Amino-1-((3R,4R,5S,6R)-4,5-dihydroxy-6-hydroxymethyl-tetrahydro-pyran-3-yl)-1H-pyrimidin-2-one

Conditions	Yield
Multi-step reaction with 7 steps 1: 69 percent / NaH / dimethylformamide / 120 °C 2: DMAP / pyridine / 83 h / Ambient temperature 3: NaOH / H2O; ethanol / 60 °C 4: pyridine / Ambient temperature 5: POCl3 / triethylamine; acetonitrile 6: NH3 / dioxane 7: H2O; acetic acid / 80 °C View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 1-((3R,4R,5S,6R)-4,5-Dihydroxy-6-hydroxymethyl-tetrahydro-pyran-3-yl)-4-hydroxy-1H-pyrimidin-2-one

Conditions	Yield
Multi-step reaction with 4 steps 1: 69 percent / NaH / dimethylformamide / 120 °C 2: DMAP / pyridine / 83 h / Ambient temperature 3: NaOH / H2O; ethanol / 60 °C 4: H2O; acetic acid / 80 °C View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 1,5-anhydro-2-deoxy-2-(uracil-1-yl)-D-altro-hexitol

Conditions	Yield
Multi-step reaction with 2 steps 1: 69 percent / NaH / dimethylformamide / 120 °C 2: 73 percent / H2O; acetic acid / 80 °C View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → 1-((3R,4R,5S,6R)-4,5-Dihydroxy-6-hydroxymethyl-tetrahydro-pyran-3-yl)-4-hydroxy-5-iodo-1H-pyrimidin-2-one

Conditions	Yield
Multi-step reaction with 6 steps 1: 69 percent / NaH / dimethylformamide / 120 °C 2: DMAP / pyridine / 83 h / Ambient temperature 3: NaOH / H2O; ethanol / 60 °C 4: pyridine / Ambient temperature 5: ICl / CH2Cl2 / Heating 6: 1.) NH3, 2.) H2O / 1.) MeOH, 2.) AcOH, 80 deg C View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → Acetic acid (4aR,7R,8R,8aS)-7-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-8-yl ester (181711-39-7)

Conditions	Yield
Multi-step reaction with 4 steps 1: 69 percent / NaH / dimethylformamide / 120 °C 2: DMAP / pyridine / 83 h / Ambient temperature 3: NaOH / H2O; ethanol / 60 °C 4: pyridine / Ambient temperature View Scheme

1,5:2,3-anhydro-4,6-O-benzylidene-D-allitol (109428-30-0) → Acetic acid (4aR,7R,8R,8aS)-7-(4-amino-2-oxo-2H-pyrimidin-1-yl)-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-8-yl ester

Conditions	Yield
Multi-step reaction with 6 steps 1: 69 percent / NaH / dimethylformamide / 120 °C 2: DMAP / pyridine / 83 h / Ambient temperature 3: NaOH / H2O; ethanol / 60 °C 4: pyridine / Ambient temperature 5: POCl3 / triethylamine; acetonitrile 6: NH3 / dioxane View Scheme

Relevant articles and documents

Synthesis of 1,5-anhydro-2-(N6-cyclopentyladenin-9-yl)-2-deoxy-D- altrohexitol

The N6-cyclopentyladenosine (CPA) analogue (4) was synthesized in 10 steps starting from glucose. The results of the radioligand binding assays are consistent with the thus far published findings that compounds containing a six-membered moiety at N9 exhibit extremely weak affinity for adenosine receptors. Replacement of the ribofuranosyl moiety of CPA (2) by a 2-deoxy-D-altrohexitol moiety is sufficient to completely abolish its agonist activity.

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