1. Product Overview
3,6-Di-O-acetyl-D-glucal (CAS 63914-23-8), also known as D-Glucal 3,6-diacetate, is a partially protected glycal derived from D-glucose. It features a 1,2-unsaturated pyranose ring (enol ether) with acetate protecting groups at the 3- and 6-positions and a free secondary hydroxyl at C-4. This stereodefined glycal is a cornerstone substrate in carbohydrate chemistry, serving as a glycosyl donor precursor via the Ferrier rearrangement (II → 2,3-unsaturated glycosides) or as a dienophile in hetero-Diels–Alder reactions. It is extensively used in the stereoselective synthesis of oligosaccharides, C-glycosides, and glycoconjugate mimetics.
2. Key Features and Benefits
• Ferrier Rearrangement Ready: Upon activation with Lewis acids (e.g., SnCl₄, BF₃·Et₂O, TMSOTf), undergoes stereoselective rearrangement to afford 2,3-unsaturated α- or β-glycosides—key intermediates for amino sugar and sialic acid analogs.
• Orthogonal Protecting Groups: The C-4 free OH allows selective functionalization; acetates at C-3/C-6 can be removed under mild basic conditions (K₂CO₃/MeOH) without affecting the enol ether.
• High Stereochemical Integrity: Derived from natural D-glucose, providing a chiral pool starting material with defined 4C₁ conformation for predictable stereochemical outcomes in glycosylation.
• Excellent Crystallinity & Stability: Forms colorless needles (mp 68–70 °C), easy to purify by recrystallization, and stable under refrigeration for extended periods.
• Versatile Reactivity: Participates in NIS/triflate-promoted glycosidation, Pd-catalyzed allylic substitutions, and iodocyclizations for accessing branched-chain sugars.
3. Major Applications
• Oligosaccharide Synthesis: Used as a glycal donor in chemoenzymatic and total chemical synthesis of N-linked glycan fragments, blood group antigens, and bacterial polysaccharide mimics.
• C-Glycoside Preparation: Via Ferrier or Danishefsky-type protocols to generate C-aryl and C-alkyl glycosides relevant to antitumor anthracyclines and natural product libraries.
• Glycoconjugate & Neoglycoprotein Design: The unsaturated bond can be further elaborated for attachment to peptides, lipids, or solid supports.
• Methodology Development: Standard substrate for testing new glycosylation promoters (IDCP, NIS/AgOTf, Au(I) catalysts) and studying anomeric effect / stereoselectivity.
• Medicinal Chemistry: Building block for designing glucosidase inhibitors and glycolipid-based vaccine adjuvants.
4. Technical Specifications
Item Description
Product Name 3,6-Di-O-acetyl-D-glucal
Synonyms D-Glucal 3,6-diacetate; 1,5-Anhydro-2-deoxy-3,6-di-O-acetyl-D-erythro-hex-1-enitol; 3,6-Di-O-acetyl-1,2-dideoxy-D-arabino-hex-1-enopyranose
CAS Number 63914-23-8
Molecular Formula C₁₀H₁₄O₆
Molecular Weight 230.21 g/mol
MDL Number MFCD00063227
Beilstein Ref 91191
Assay (Purity) ≥95% (GC/HPLC); Typical high-grade ≥98%
Appearance White to off-white crystalline solid or needles
Melting Point 68–70 °C (Literature)
Boiling Point ~334.5 °C (Predicted)
Optical Rotation [α]D²⁰ ≈ -29° to -33° (c = 1, CHCl₃)
Density ~1.28 g/cm³ (Predicted)
Solubility Soluble: CHCl₃, DCM, Toluene, THF, Acetone, EtOAc, Hot EtOH.
Slightly soluble: Cold EtOH, MeOH.
Practically insoluble: Water (hydrolyzes slowly in acidic aq.).
pKa (Phenolic OH equiv.) ~13.3 (Predicted, for aliphatic OH)
SMILES CC(=O)OC[C@H]1C[C@@H](OC(=O)C)/C=C/O1
InChI Key ecco — see database: RUVKXRADZFDTIG-WCBMZIALSA-N
Storage (Powder) 2–8 °C, sealed, protected from light & moisture; stable ≥24 months
HS Code 2940.00.90 (or 2932.99.90 depending on customs)
5. Storage and Handling
• Storage: Store in a tightly sealed container at 2–8 °C, protected from light. For long-term storage (>12 months), keep in a desiccator. The enol ether is stable under these conditions but may slowly hydrolyze in the presence of acid or prolonged moisture exposure.
• Handling: Allow vial to reach ambient temperature before opening to prevent moisture condensation. Dissolve in dry DCM, CHCl₃, or THF. Avoid prolonged contact with strong Lewis/Brønsted acids unless initiating a reaction.
• Deprotection: Acetate groups can be cleanly removed with 0.1 M NaOMe/MeOH or K₂CO₃/MeOH at 0 °C → RT; monitor by TLC. The glycal enol ether is generally stable to these mild base conditions.
• Solution Stability: Prepare fresh for critical glycosylations; DMSO stocks may degrade over time. Avoid heating above 50 °C in protic solvents.
6. Safety Summary (Full SDS Highlights)
• GHS Classification: GHS07 – Warning
• Signal Word: Warning
• Hazard Statements:
• H315: Causes skin irritation.
• H319: Causes serious eye irritation.
• H335: May cause respiratory irritation.
• (Not classified as acutely toxic or mutagenic)
• Precautionary Statements:
• P261: Avoid breathing dust/mist/vapors. Use only in a well-ventilated area or fume hood.
• P264: Wash hands, forearms, and face thoroughly after handling.
• P270: Do not eat, drink, or smoke in areas where this material is used.
• P271: Use only outdoors or in a well-ventilated area.
• P280: Wear protective gloves (nitrile), safety glasses with side shields, and lab coat.
• P301+P312: IF SWALLOWED: Call a POISON CENTER or physician if you feel unwell.
• P302+P352: IF ON SKIN: Wash with plenty of soap and water.
• P304+P340: IF INHALED: Remove person to fresh air and keep comfortable for breathing.
• P305+P351+P338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses if present and easy to do. Continue rinsing.
• P330: Rinse mouth if swallowed.
• P337+P313: If eye irritation persists: Get medical advice/attention.
• P403+P233: Store in a well-ventilated place. Keep container tightly closed.
• P501: Dispose of contents/container in accordance with local, regional, and national regulations.
• First Aid Measures:
• Inhalation: Remove to fresh air. If breathing difficult, administer oxygen and seek medical attention.
• Skin Contact: Immediately wash with plenty of soap and water. Remove contaminated clothing. Seek medical advice if irritation or rash develops.
• Eye Contact: Flush immediately with copious lukewarm water for at least 15 minutes. Remove contact lenses if possible. Seek medical attention.
• Ingestion: Rinse mouth. Do NOT induce vomiting. Give water to drink if conscious. Seek medical advice.
• Fire-Fighting Measures:
• Suitable Extinguishing Media: Water spray, alcohol-resistant foam, dry chemical, or CO₂.
• Special Hazards: Combustion may produce irritating/acrid smoke (acetic acid vapor, CO).
• Protective Equipment: Wear self-contained breathing apparatus (SCBA) and full protective clothing.
• Spill Response:
• Avoid dust generation. Sweep up and place in a suitable closed container for disposal. Do not allow entry to drains or waterways. Ventilate area after cleanup.
• Handling & Storage:
• Handle in fume hood. Keep container closed when not in use. Store cool (2–8 °C), dry, and away from strong oxidizers and strong acids.
• Intended Use: For laboratory research and development ONLY. Not for human or veterinary therapeutic, diagnostic, or food use.
