630-580-1088 sales@ambeed.com
Structure Search

List Search MOL Search Structure Search

0
Chemistry
Asymmetric Synthesis >>Chiral Building BlocksChiral Catalysts, Chiral Ligands and Chiral ReagentsChiral Resolution ReagentsBoronic acids/esters >>Aliphatic BoronsAromatic BoronsOther BoronsOxaborolesCatalysis Chemistry >>Achiral Crown LigandsC-H ActivationCarbon-Donor LigandsChiral Carbon LigandsChiral Crown LigandsChiral Olefin LigandsCross-CouplingCross-Coupling Using Transition Metal CatalystsDACH or Trost LigandsChemical Biology >>Conjugation Chemistry
GlycoscienceLinkers and CrosslinkersNucleic Acid ChemistryPEGylationPeptide ChemistryPhotolabile Protecting GroupHeterocyclic Building Blocks >>AcridinesAliphatic HeterocyclesAromatic HeterocyclesAzetidinesBenzimidazolesBenzisoxazolesBenzodioxansBenzofuransBenzothiazolesInorganic reagents >>Inorganic ReagentOrganic Building Blocks >>Acid AnhydridesAcyl Chlorides
AlcoholsAldehydesAliphatic Chain HydrocarbonsAliphatic Cyclic HydrocarbonsAlkenesAlkylsAlkynesOrganometallic Reagents >>Grignard ReagentsOrganoarsenicOrganobismuthOrganoboronOrganogermaniumOrganolithiumOrganomercuryOrganosiliconOrganotinSpecialty Synthesis >>Enzyme-Mediated SynthesisFluorous SynthesisIonic Liquids
Solid Supported SynthesisStains and Dyes >>Acid DyesAzoic DyesBasic DyesDirect DyesDisperse DyesDye IntermediatesMordant DyesOil DyesOther Stains and DyesSynthetic Reagents >>Acids and BasesC-C Bond FormationC-X Bond Formation (Halogen)C-X Bond Formation (Non-Halogen)Chelation and Complexation CompoundsCondensation AgentsCouplingDehydrating ReagentsFluorination Reagent
Pharmaceutical Intermediates
Analgesics >>BenzhydrocodoneBicifadineCapsaicinCelecoxibDebio-0827DexamethasoneElagolix SodiumEsketamine HydrochlorideIbuprofen SodiumAnesthetics >>CiprofolEsketamine HydrochlorideFospropofol Fospropofol DisodiumLevobupivacaine RemimazolamRemimazolam BesilateRemimazolam BesylateRopivacaineAnti-Addiction Agents >>Kakonein
Lofexidine HydrochlorideVarenicline Anti-inflammatory Agents >>ApremilastAsunaprevirATB-346 RelatedBalsalazide BaricitinibBencycloquidium BromideBudesonideCefiderocol Sulfate TosylateCeftaroline Fosamil AcetateAntibacterials >>AFN-1252 RelatedAlatrofloxacin Bedaquiline FumarateBesifloxacin BrilacidinCaspofungin AcetateCefiderocol Sulfate TosylateCefilavancinCeftaroline Fosamil
Anticonvulsants >>BrivaracetamCannabidiolEscitalopram OxalateEslicarbazepine Acetate RelatedFosphenytoinGabapentin EnacarbilJNJ-10234094LacosamideLevetiracetam RelatedAntidementia Agents >>Azeliragon RelatedDavunetideDonepezil HydrochlorideDonepezil RelatedEnsaculinFlorbetaben Flortaucipir F 18Flutemetamol IdalopirdineAntidepressants >>4-Chlorokynurenine
AgomelatineAgomelatine RelatedAllopregnanolone RelatedAmibegronAmitifadineAripiprazole RelatedBasimglurantBefloxatoneAntiemetics >>AprepitantAprepitant RelatedDolasetron RelatedDolasetron Mesylate HydrateFosaprepitant DimeglumineFosaprepitant RelatedOlanzapinePalonosetron RelatedPalonosetron HydrochlorideAntifungals >>Anidulafungin RelatedCabotegravirMore >>
Inhibitors/Agonists
ADC >>ADC AntibodyADC LinkerADC Linker with PayloadADC ToxinAntibody-Drug Conjugates (ADCs)Drug-Linker Conjugates for ADCAngiogenesis >>ALKBcr-AblBTKEGFRFAKFGFRFLT3HER2HIFAnti-infection >>3CLproAntibacterialAntibioticAntifungal
AntiparasiticAntiprotozoalAntiviralArenavirusBVDVApoptosis >>Apoptosis InducerBcl-2Bcl-6BRKc-Mycc-RETC/EBPCARDCaspaseAutophagy >>Atg4ATG4BATTECsAUTACsAutophagyBeclin1
FKBPLC3LRRK2Biochemical Reagent >>Cell Cycle >>AntifolateAPCAurora KinaseBUBCasein KinaseCdc25CDKChkCRISPR/Cas9Cytoskeleton >>ActinArp2/3 ComplexCYTHCytoplasmic DyneinDynaminFAKMore >>
Material Science
Aggregation-Induced Emission >>Other AIE BlocksTetraphenylethylene SeriesCOFs Linkers >>Aldehyde COFs LinkersAlkynyl COFs LinkersAmine COFs LinkersBoric COFs LinkersCyano COFs LinkersMultifunctional COFs linkersOther COFs linkersTriptycene SeriesElectronic Materials >>Battery MaterialsDye-Sensitized Solar Cell (DSSC) MaterialsElectronic MaterialLiquid Crystal (LC) MaterialsMolecular ConductorsOrganic Light-Emitting Diode (OLED) MaterialsOrganic Solar Cell (OPV) MaterialsOrganic Transistor (OFET) MaterialsPerovskite Solar Cell (PSC) MaterialsMagnetic Materials >>Magnetic Ionic LiquidsMagnetic MaterialMagnetic Metal Complexes
Organic Radicals Material Chemical Compounds >>Ligands for Functional Metal ComplexesLiquid Crystal (LC) Building BlocksPhthalocyanine Building BlocksPolymer and Macromolecule Semiconductor Building BlocksSmall Molecule Semiconductor Building BlocksSolubility Enhancing Reagents Supramolecular Host Materials MOF Ligands >>Carboxylic Acid MOF LigandsCarboxylic Acid Nitrogen-Containing Mixed MOF LigandsNitrogen-Containing MOF LigandsOther MOF LigandsNanomaterials >>Carbon NanomaterialsCeramic MembranesDendrimersGold NanoparticlesIron Oxide NanoparticlesMaterials by ApplicationMesoporous MaterialsMetals and Metal AlloysNano Minerals: NanoclaysOLED Materials >>Dopant
HostHTMOLED IntermediatesOther OLED related materialsOptical Materials >>Coumarin DyesCyanine and Squarylium DyesDCM DyesDipyrromethene DyesFluorescence MaterialsFluorescent ProbesHeat and Pressure Sensitive DyesNear-Infrared (NIR) DyesOrganic Non-Linear Optical (NLO) MaterialsOrganic Pigments >>Organic PigmentOther Materials >>Mateial OtherPolymer Science >>MonomersPolymer AdditivesPolymerization ReagentsPolymersResins
Contact Us
Home Cart 0 Sign in  
Chemistry
Heterocyclic Building Blocks
Tetrahydropyrans
2-tetrahydropyranyl
(2R,3S,4S,5R,6R)-6-(Acetoxymethyl)tetrahydro-2H-pyran-2,3,4,5-tetrayl tetraacetate
Chemistry
Heterocyclic Building Blocks
Chemical Biology
Tetrahydropyrans
Glycoscience
2-tetrahydropyranyl

[ CAS No. 4163-65-9 ] {[proInfo.proName]}

,{[proInfo.pro_purity]}
Cat. No.: {[proInfo.prAm]}
Chemical Structure| 4163-65-9
Chemical Structure| 4163-65-9
Structure of 4163-65-9 * Storage: {[proInfo.prStorage]}
Cart0 Add to My Favorites Add to My Favorites Bulk Inquiry Inquiry Add To Cart

Search after Editing

* Storage: {[proInfo.prStorage]}

For Research Only 110K+ Compounds Competitive Price 1-2 Day Shipping

Quality Control of [ 4163-65-9 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 4163-65-9 ]

SDS Specification
Alternatived Products of [ 4163-65-9 ]

Product Details of [ 4163-65-9 ]

CAS No. :4163-65-9 MDL No. :MFCD00069798
Formula : C16H22O11 Boiling Point : -
Linear Structure Formula :- InChI Key :LPTITAGPBXDDGR-OWYFMNJBSA-N
M.W : 390.34 Pubchem ID :11741089
Synonyms :

Calculated chemistry of [ 4163-65-9 ]

Physicochemical Properties

Num. heavy atoms : 27
Num. arom. heavy atoms : 0
Fraction Csp3 : 0.69
Num. rotatable bonds : 11
Num. H-bond acceptors : 11.0
Num. H-bond donors : 0.0
Molar Refractivity : 84.42
TPSA : 140.73 Ų

Pharmacokinetics

GI absorption : Low
BBB permeant : No
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : Yes
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -8.23 cm/s

Lipophilicity

Log Po/w (iLOGP) : 3.32
Log Po/w (XLOGP3) : 0.63
Log Po/w (WLOGP) : -0.37
Log Po/w (MLOGP) : -0.6
Log Po/w (SILICOS-IT) : 0.03
Consensus Log Po/w : 0.6

Druglikeness

Lipinski : 1.0
Ghose : None
Veber : 2.0
Egan : 1.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -1.93
Solubility : 4.58 mg/ml ; 0.0117 mol/l
Class : Very soluble
Log S (Ali) : -3.16
Solubility : 0.27 mg/ml ; 0.000691 mol/l
Class : Soluble
Log S (SILICOS-IT) : -0.57
Solubility : 104.0 mg/ml ; 0.267 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 4.79

Safety of [ 4163-65-9 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 4163-65-9 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 4163-65-9 ]

[ 4163-65-9 ] Synthesis Path-Downstream   1~36

  • 1
  • [ 3458-28-4 ]
  • [ 108-24-7 ]
  • β-D-mannopyranose pentaacetate [ No CAS ]
  • [ 4163-65-9 ]
YieldReaction ConditionsOperation in experiment
at 28 - 32℃; for 0.25h;
With pyridine at 20℃; Inert atmosphere; Overall yield = 88%; Overall yield = 1.91 g;
13 % de With pyridine at 20℃; for 4h; Overall yield = 93 %; Overall yield = 403 mg; 1,2,3,4,6-Penta-O-acetyl-α/β-d-mannopyranose (10c) D-Mannose (200.0 mg, 1.11 mmol), pyridine (2.2 mL), and acetic anhydride (1.1 mL, 11.1 mmol) were combined in a round-bottom flask and stirred at room temperature for 4 h until starting material was completely consumed. The reaction mixture was diluted with ice-water and extracted with EtOAc. The organic layers were combined and washed with 1 M HCl, water, saturated aqueous NaHCO3 and brine sequentially, dried over anhydrous Na2SO4, concentrated in vacuo. The residue was purified by silica gel chromatography to give 10c (403 mg, 93%, anomeric mixture, α:β = 1:1.3) as a colorless syrup.
With sulfuric acid at -5 - 40℃; for 0.5h; Overall yield = 81.7 %; Overall yield = 8.9 g;
42.857 % de With sodium acetate at 80℃; for 4h; Inert atmosphere; Overall yield = 85 %; Overall yield = 3.5 g; 6 EXAMPLE 6 Alternative synthesis of Benzoylated Propargyl Mannose (5) 1,2,3,4,6-penta-O-acetyl-D-mannopyranose (6) Acetic anhydride (20.7 mL, 160 mmol) was added to a mixture of -mannose (3.0 (0147) D (0148) g, 10.6 mmol) and sodium acetate (1.6 g, 20 mmol). The reaction mixture was then stirred at 80^C for 4 h. and poured into cold sat. NaHCO3 solution (100 mL). The mixture was then stirred for 1 h., extracted with DCM (2 × 100 mL), dried (MgSO ) and concentrated (0149) 4 (0150) under reduced pressure. The pentaacetate 6 (3.5 g, 85%, α/β 1:0.4) was obtained as a colorless oil. The crude material was used in the subsequent step without further purification.1H NMR (CDCl , 400 MHz): 6.06 (d, 1H, J = 1.1 Hz), 5.84 (d, 0.4 H, J = 1.3 (0151) 3 (0152) Hz), 5.46 (dd, 0.4H, J = 1.1 Hz, J = 3.3 Hz), 5.34-5.32 (m, 2H), 5.28 (d, 0.4H, J = 9.9 Hz), 5.25-5.22 (m, 1H), 5.11 (dd, 0.4H, J = 3.3 Hz, J = 10.0 Hz), 4.28 (dd, 0.4H, J = 5.4 Hz, J = 12.5 Hz), 4.26 (dd, 1H, J = 4.9 Hz, J = 12.3 Hz), 4.15-3.98 (m, 2.4H), 3.78 (ddd, 0.4H, J = 2.4 Hz, J = 5.3 Hz, J = 7.8 Hz), 2.19 (s, 1.2H, OCH ), 2.16 (s, 3H, OCH ), 2.15 (s, 3H, (0153) 3 3 (0154) OCH ), 2.08 (s, 1.3H, OCH ), 2.07 (s, 4H, OCH ), 2.03 (s, 4H, OCH ), 1.99 (s, 4H, 3 3 3 3 (0155) OCH3).
33.333 % de With iodine at 0 - 20℃; for 4h; Overall yield = 98 %; Overall yield = 54 g; 1,2,3,4,6-Penta-O-acetyl-α/β-D-mannopyranose (i) [3] To a solution of D-mannose (25.0 g, 0.139 mol) in Ac2O (125 mL,1.318 mol) at 0 °C was added I2 (1.4 g, 5.5 mmol). The reaction mixture was left to stir for 4 h at ambient temperature, then quenched with saturatedNa2SO3 (0.7 g, 5.5 mmol) and NaHCO3, until no more CO2 evolved and the solutionbecame colorless. The organic product was extracted with CH2Cl2 (3 × 100 mL), and thecollected organic layers were washed with NaHCO3 (100 mL), dried over Na2SO4 andconcentrated under reduced pressure with toluene azeotrope to afford a clear viscousoil (54.0 g, 0.14 mol, 98%, 2:1 mixture :). The product was used without furtherpurification.
With pyridine at 20℃; for 96h; Overall yield = 86 %;

Reference： [1]Dasgupta, Falguni; Singh, Prem P.; Srivastava, Harish H. [Carbohydrate Research, 1980, vol. 80, p. 346 - 349]
[2]Andersen, Sofie Meng; Heuckendorff, Mads; Jensen, Henrik H. [Organic Letters, 2015, vol. 17, # 4, p. 944 - 947]
[3]Xu, Yang; Zhang, Qian; Xiao, Ying; Wu, Pinru; Chen, Wei; Song, Zejin; Xiao, Xiong; Meng, Lingkui; Zeng, Jing; Wan, Qian [Tetrahedron Letters, 2017, vol. 58, # 24, p. 2381 - 2384]
[4]Hollas, Michael A.; Webb, Simon J.; Flitsch, Sabine L.; Fielding, Alistair J. [Angewandte Chemie - International Edition, 2017, vol. 56, # 32, p. 9449 - 9453][Angew. Chem., 2017, vol. 129, # 32, p. 9577 - 9581,5]
[5]Current Patent Assignee: GLYCOSYNNOVATIONS; COOMBE - WO2018/68090, 2018, A1 Location in patent: Paragraph 0187; 0213
[6]Rintelmann, Chelsea L.; Grinnage-Pulley, Tara; Ross, Kathleen; Kabotso, Daniel E.K.; Toepp, Angela; Cowell, Anne; Petersen, Christine; Narasimhan, Balaji; Pohl, Nicola [Beilstein Journal of Organic Chemistry, 2019, vol. 15, p. 623 - 632]
[7]Pettenuzzo, Nicolò; Brustolin, Leonardo; Coltri, Elisa; Gambalunga, Alberto; Chiara, Federica; Trevisan, Andrea; Biondi, Barbara; Nardon, Chiara; Fregona, Dolores [ChemMedChem, 2019, vol. 14, # 12, p. 1162 - 1172]
  • 2
  • [ 92254-28-9 ]
  • [ 4163-65-9 ]
  • [ 171905-61-6 ]
YieldReaction ConditionsOperation in experiment
With boron trifluoride diethyl etherate In 1,2-dichloro-ethane Ambient temperature;
Reference： [1]Kogan, Timothy P.; Dupre, Brian; Keller, Karin M.; Scott, Ian L.; Bui, Huong; et al. [Journal of Medicinal Chemistry, 1995, vol. 38, # 26, p. 4976 - 4984]
  • 3
  • [ 4163-65-9 ]
  • [ 13242-53-0 ]
YieldReaction ConditionsOperation in experiment
100% With hydrogen bromide; acetic acid for 4h; Ambient temperature;
100% With hydrogen bromide In dichloromethane; acetic acid at 0 - 20℃; 2.2 3.2.2. 2,3,4,6-Tetra-O-acetyl-α-d-mannopyranosyl bromide (1).16b To a solution of 1,2,3,4,6-penta-O-acetyl-α-d-mannopyranose (9.98 g, 25.6 mmol, 1.0 equiv) in CH2Cl2 (120 mL) at 0 °C was added slowly a solution of HBr (150 mL, 33 wt % in acetic acid) and the solution was allowed to warm up to room temperature. The solution was then stirred for 3 h and diluted with water (100 mL). The two phases were separated and the aqueous layer was extracted with CH2Cl2 (3*75 mL). The combined organic layers were washed with a saturated aqueous solution of NaHCO3 (with care, very exothermic) until neutral pH, and then with brine (50 mL). The organic layer was then dried over MgSO4, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel (PE/EtOAc: 6:4) to afford the brominated compound 1 (10.50 g, quant.) as a yellow waxy solid. 1H NMR (400 MHz, CDCl3) δ 6.28 (d, J=1.6 Hz, 1H), 5.70 (dd, J=10.2, 3.4 Hz, 1H), 5.43 (dd, J=3.4, 1.6 Hz, 1H), 5.35 (t, J=10.2 Hz, 1H), 4.31 (dd, J=12.6, 5.0 Hz, 1H), 4.21 (ddd, J=10.2, 5.0, 2.3 Hz, 1H), 4.12 (dd, J=12.6, 2.3 Hz, 1H), 2.16 (s, 3H), 2.09 (s, 3H), 2.06 (s, 3H), 1.99 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 170.6 (s), 169.8 (s), 169.7 (2s), 83.2 (d), 72.9 (d), 72.2 (d), 68.0 (d), 65.4 (d), 61.6 (t), 20.9 (q), 20.8 (2q), 20.7 (q).
99% With hydrogen bromide; acetic anhydride In acetic acid at 20℃; for 4.5h;
98% With hydrogen bromide In dichloromethane; acetic acid at 0 - 20℃;
95% With hydrogen bromide In dichloromethane; acetic acid at 0 - 25℃; for 20h;
90% With boron trifluoride diethyl etherate; hydrogen bromide; acetic acid In dichloromethane at 0 - 20℃; for 2h; 2,3,4,6-Tetra-O-acetyl-1-S-acetyl-β-D-mannopyranose 13 To a solution of penta-O-acetyl-D-mannopyranose 11 (1.00 g,2.56 mmol) in DCM (10 mL) was added HBr-AcOH (33%, 15 mL) at 0 C. After the reaction proceeded for two hours, the mixture was extracted and concentrated, giving 2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl bromide 12 (946 mg, 90%), which could be used in the next step without further purification. To a solution of 12(700 mg, 2.6 mmol) in toluene (10 mL) was added TBASAc (1.65 g,5.2 mmol). The reaction proceeded for 5 h at room temperature. After extracted and concentrated, the resulting residue was purified by flash chromatography (ethyl acetate/petrol; 1:2) to afford compound 13 (589 mg, 85%).
80% With hydrogen bromide; acetic acid for 2h; Inert atmosphere;
93 % Spectr. With trimethylsilyl bromide In dichloromethane
With hydrogen bromide; acetic acid at 20℃; for 14h;
With hydrogen bromide In acetic acid 4 The commercial peracetylated mannose 1 (i.e. 1,2,3,4,5-penta-O-acetyl-α-D-mannopyranose) is brominated in the anomeric position by the action of hydrogen bromide in acetic acid, as described by A. LEVENE et al. in J. Biol. Chem., 1931, 90, 89-98. The activated intermediate 2 is cyclized to the orthoester 3 in a 2,6-dimethylpyridine/methanol mixture. The regioselective opening of the orthoester by acid hydrolysis at 0° C. in a 10% aqueous trifluoroacetic acid/acetonitrile mixture produces 1,3,4,6-tetra-O-acetyl-β-D-mannopyranose (5). The regioisomer 4 is also isolated.
With hydrogen bromide; acetic acid In dichloromethane at 20℃; for 2h; 1-A Preparation of bromide 1-A To a solution of 1,2,3,4,6-penta-O-acetyl-D-mannopyra- nose (1 g, 2.56 mmol) in DCM (2 mL) was added HBr (33% in AcOR, 2.5 mL) dropwise at room temperature. The reac65 tion mixture was stirred at room temperature for 2 h. Themixture was diluted with DCM, and washed with H20 andNaHCO3 (3x). The organic layer was dried and concentrated. 25The crude 1-A (1.06 g, 100%) was pure enough to he used directly in the next step without thrther purification.
11.9 g With hydrogen bromide; acetic acid at 20℃; for 1h; Preparation of 1-bromo-2,3,4,6-tetra-Oacetyl-α-D-mannopyranose 1 10 g of α-D-mannose pentaacetate are dissolved in 20 ml of a solution of hydrobromic acid at 33% in acetic acid. The yellow solution is stirred for 1 h at ambient temperature. The reaction mixture is cooled to 0° C., diluted with 30 ml of CH2Cl2 and neutralized using a saturated solution of NaHCO3. The aqueous phase is extracted with CH2Cl2 (5×100 ml). The organic phases are combined, dried over MgSO4 and concentrated so as to give the compound 1 (11.9 g) which is used for the next step without purification. C14H19BrO9 Chemical formula 1: Exact weight: 410.02 g·mol-1 Rf: 0.76 [EtOAc/Cyclo (1:1)]
With hydrogen bromide; acetic acid In dichloromethane at 0 - 20℃; for 2h;

Reference： [1]Abbott, Shaun D.; Gagnon, Lyne; Lagraoui, Mouna; Kadhim, Salam; Attardo, Giorgio; Zacharie, Boulos; Penney, Christopher L. [Journal of Medicinal Chemistry, 1998, vol. 41, # 11, p. 1909 - 1926]
[2]Bensoussan, Charlélie; Rival, Nicolas; Hanquet, Gilles; Colobert, Françoise; Reymond, Sébastien; Cossy, Janine [Tetrahedron, 2013, vol. 69, # 36, p. 7759 - 7770]
[3]Ella-Menye, Jean-Rene; Nie, Xiaoping; Wang, Guijun [Carbohydrate Research, 2008, vol. 343, # 10-11, p. 1743 - 1753]
[4]Appeldoorn, Chantal C.M.; Joosten, John A.F.; Ait El Maate, Fatna; Dobrindt, Ulrich; Hacker, Joerg; Liskamp, Rob M.J.; Khan, A. Salam; Pieters, Roland J. [Tetrahedron Asymmetry, 2005, vol. 16, # 2, p. 361 - 372]
[5]Location in patent: experimental part Haider, Anita; Williams, Charlotte K. [Comptes Rendus Chimie, 2011, vol. 14, # 7-8, p. 736 - 744]
[6]Wu, Bin; Ge, Jiantao; Ren, Bo; Pei, Zhichao; Dong, Hai [Tetrahedron, 2015, vol. 71, # 23, p. 4023 - 4030]
[7]Wendeln, Christian; Rinnen, Stefan; Schulz, Christian; Kaufmann, Tobias; Arlinghaus, Heinrich F.; Ravoo, Bart Jan [Chemistry - A European Journal, 2012, vol. 18, # 19, p. 5880 - 5888]
[8]Cavallaro, Cullen L.; Schwartz, Jeffrey [Journal of Organic Chemistry, 1995, vol. 60, # 21, p. 7055 - 7057]
[9]Baeschlin, Daniel K.; Green, Luke G.; Hahn, Michael G.; Hinzen, Berthold; Ince, Stuart J.; Ley, Steven V. [Tetrahedron Asymmetry, 2000, vol. 11, # 1, p. 173 - 197]
[10]Current Patent Assignee: INSTITUT PASTEUR - US2006/67888, 2006, A1 Location in patent: Page/Page column 11; sheet 7
[11]Current Patent Assignee: DEMERX INC - US8637648, 2014, B1 Location in patent: Page/Page column 24; 25
[12]Current Patent Assignee: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; UNIVERSITY OF MONTPELLIER; NANOMEDSYN - US2018/265534, 2018, A1 Location in patent: Paragraph 0161; 0162; 0163
[13]Han, Liwen; Sheng, Wenlong; Li, Xiaobin; Sik, Attila; Lin, Houwen; Liu, Kechun; Wang, Lizhen [MedChemComm, 2019, vol. 10, # 4, p. 598 - 605]
  • 4
  • [ 126-00-1 ]
  • [ 4163-65-9 ]
  • 4,4-Bis-[4-((2R,3S,4S,5R,6R)-3,4,5-triacetoxy-6-acetoxymethyl-tetrahydro-pyran-2-yloxy)-phenyl]-pentanoic acid [ No CAS ]
YieldReaction ConditionsOperation in experiment
With boron trifluoride diethyl etherate In 1,2-dichloro-ethane
Reference： [1]Kogan, Timothy P.; Dupré, Brian; Bui, Huong; McAbee, Kathy L.; Kassir, Jamal M.; Scott, Ian L.; Hu, Xin; Vanderslice, Peter; Beck, Pamela J.; Dixon, Richard A. F. [Journal of Medicinal Chemistry, 1998, vol. 41, # 7, p. 1099 - 1111]
  • 5
  • [ 7217-59-6 ]
  • [ 4163-65-9 ]
  • [ 220691-84-9 ]
YieldReaction ConditionsOperation in experiment
100% With boron trifluoride diethyl etherate; In dichloromethane; at 0 - 20℃; for 12.5h; To a solution of D-mannose pentaacetate (38) (1.20 g,3.07 mmol) and o-MeOC6H4SH (0.49 mL, 4.0 mmol) in CH2Cl2(30 mL) at 0 C was added BF3OEt2 (1.90 mL, 15.4 mmol), and theresultant solution was stirred at 0 C for 30 min and then at roomtemperature for 12 h. The reaction was quenched with saturatedaqueous NaHCO3 solution at 0 C. The resultant mixture was dilutedwith EtOAc, washed with H2O and brine, dried (Na2SO4),filtered, and concentrated under reduced pressure. Purification of the residue by flash column chromatography (silica gel, 10e40%EtOAc/hexanes) gave thioglycoside 39 (1.49 g, quant, dr >20:1) asa yellowoil: [a]D24 122.8 (c 1.00, CHCl3); IR (film) 2942, 1749, 1370,1245, 1227, 1063 cm1; 1H NMR (600 MHz, CDCl3) d 7.45 (dd, J7.8,1.8 Hz, 1H), 7.26 (m, 1H), 6.90e6.86 (m, 2H), 5.61 (d, J1.4 Hz, 1H),5.49 (dd, J3.7, 1.8 Hz, 1H), 5.41 (dd, J9.7, 3.2 Hz, 1H), 5.30 (dd,J10.1, 10.1 Hz, 1H), 4.48 (ddd, J10.1, 5.5, 2.3 Hz, 1H), 4.25 (dd,J12.4, 5.5 Hz, 1H), 3.96 (dd, J12.4, 2.3 Hz, 1H), 3.86 (s, 3H), 2.13(s, 3H), 2.04 (s, 3H), 1.98 (s, 3H), 1.97 (s, 3H); 13C NMR (150 MHz,CDCl3) d 170.6, 169.9, 169.8 (2C), 158.7, 134.0, 129.9, 121.1, 119.4,111.0, 83.1, 70.8, 69.5, 69.4, 66.3, 62.3, 55.8, 20.9, 20.70, 20.66,20.63; HRMS (ESI) calcd for C21H26O10SNa [(MNa)] 493.1139,found 493.1143.
Reference： [1]Organic Letters,2015,vol. 17,p. 366 - 369
[2]Tetrahedron,2015,vol. 71,p. 6369 - 6383
[3]Journal of the Chemical Society. Perkin transactions I,1998,p. 3907 - 3911
  • 6
  • [ 1095-03-0 ]
  • [ 4163-65-9 ]
  • [ 2872-72-2 ]
Reference： [1]Tetrahedron Letters,2001,vol. 42,p. 4009 - 4011
  • 7
  • [ 57641-66-4 ]
  • [ 4163-65-9 ]
  • 2-[2-(2-bromo-ethoxy)-ethoxy]-O-2',3',4',6'-tetraacetyl-α-D-mannose [ No CAS ]
Reference： [1]Journal of Medicinal Chemistry,2006,vol. 49,p. 2558 - 2567
  • 8
  • [ 4163-65-9 ]
  • [ 124650-29-9 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: SnCl4; 4 Angstroem molecular sieves / CH2Cl2 / 19 h / 20 °C 2: 2.43 g / NaOMe / methanol / 1 h
Reference： [1]Watt, Jacinta A.; Williams, Spencer J. [Organic and Biomolecular Chemistry, 2005, vol. 3, # 10, p. 1982 - 1992]
  • 9
  • [ 4163-65-9 ]
  • [ 854262-01-4 ]
Reference： [1]Organic letters,2002,vol. 4,p. 489 - 492
[2]Chemistry - A European Journal,2012,vol. 18,p. 14671 - 14679
[3]New Journal of Chemistry,2015,vol. 39,p. 4115 - 4127
[4]Chemistry - A European Journal,2016,vol. 22,p. 11450 - 11460
[5]Chemistry - A European Journal,2017,vol. 23,p. 14307 - 14315
  • 10
  • β-D-mannopyranose pentaacetate [ No CAS ]
  • [ 4163-65-9 ]
  • [ 13242-53-0 ]
YieldReaction ConditionsOperation in experiment
With hydrogen bromide In dichloromethane; acetic acid at 20℃; for 2h; 61 Example 61: 2,3,4,6-TETRA-O-ACETYL-α-D-MANNOPYRANOSOYL bromide D-Mannose pentaacetate (103 g, 264 mmol) was dissolved in anhydrous DCM (200 mL). To this hydrogen bromide (33% in acetic ACID, 200 ML) WAS ADDED. THE mixture was left under argon at RT. After a 2 h period, t. l. c. (petrol: ethyl acetate, 2: 1) indicated the formation of a product (RF 0.3) with complete consumption of the starting material (Rf 0.2). The reaction mixture was partitioned between DCM (100 ML) and ice water (200 mL), and the aqueous layer re-extracted with DCM (3 x 200 ML). The combined organic layers were washed with sodium hydrogen carbonate until pH 8 was obtained, then with brine (300 mL), dried(MgS04), filtered and concentrated in vacuo. The resulting title compound, a clear oil, (106.6 g) was used without purification; 5H (400 MHz, CDCl3) 1.96, 2.03, 2.06, 2.13 (12H, 4 x s, 4 x OAc), 4.09 (1H, dd, J5,6 2. 2 HZ, J6, 6' 12.5 Hz, H-6), 4.18 (1H, dd, J4,5 10.1 Hz, J5,6 2.2 Hz, J5,6' 4. 8 Hz, H-5), 4.28 (1H, dd, J5, 6 4.9 HZ, >6, 6' 12. 5 Hz, H-6'), 5. 32 (1H, at, J 10.1 Hz, H-4), 5. 39 (1H, dd, J1, 2 1.6 HZ, J2, 3 3.5 Hz, H-2), 5.66 (1H, dd, J2, 3 3.5 HZ, J3, 4 10. 1 Hz, H-3), 6.26 (1H, bs, H-1).
Reference： [1]Current Patent Assignee: UNIVERSITY OF OXFORD; Oxford University Innovation (in: Oxford University) - WO2005/862, 2005, A2 Location in patent: Page/Page column 71
  • 11
  • [ 3458-28-4 ]
  • [ 108-24-7 ]
  • [ 4163-65-9 ]
YieldReaction ConditionsOperation in experiment
100% With iodine at 20℃; for 1h; optical yield given as %de;
100% With pyridine; dmap at 0 - 20℃; 2.1 3.2.1. 1,2,3,4,6-Penta-O-acetyl-α-d-mannopyranose.16a To a solution of d-mannose (21.6 g, 120.0 mmol, 1.0 equiv) in acetic anhydride (62.3 mL, 660.0 mmol, 5.5 equiv) at 0 °C were added DMAP (1.46 g, 12.0 mmol, 10 mol %) and pyridine (240 mL) and the mixture was allowed to warm to room temperature. The solution was stirred for 3 h and the reaction was quenched by addition of a 10% aqueous solution of CuSO4 (250 mL) and Et2O (250 mL). The two phases were separated and the organic layer was washed with a 10% aqueous solution of CuSO4 (5*150 mL) in order to remove pyridine. The organic layer was dried over MgSO4, filtered, and concentrated under reduced pressure to afford 1,2,3,4,6-penta-O-acetyl-α-d-mannopyranose (46.5 g, quant.) as a white waxy solid. 1H NMR (400 MHz, CDCl3) δ 6.07 (d, J=1.8 Hz, 1H), 5.34-5.32 (m, 2H), 5.25-5.24 (m, 1H), 4.27 (dd, J=12.4, 4.9 Hz, 1H), 4.08 (dd, J=12.4, 2.5 Hz), 4.06-4.00 (m, 1H), 2.16 (s, 3H) 2.16 (s, 3H), 2.08 (s, 3H), 2.04 (s, 3H), 1.99 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 170.8 (s), 170.1 (s), 169.9 (s), 169.6 (s), 168.2 (s), 90.7 (d), 70.7 (d), 68.8 (d), 68.4 (d), 65.6 (d), 62.2 (t), 21.0 (q), 209.0 (q), 20.8 (3q).
100% With pyridine; dmap at 20℃; Inert atmosphere;
100% With pyridine; dmap at 0 - 20℃;
80.4% With sulfuric acid at 0 - 20℃; for 0.666667h;

Reference： [1]Location in patent: scheme or table Jalsa, Nigel Kevin; Singh, Gurdial [Tetrahedron Asymmetry, 2009, vol. 20, # 6-8, p. 867 - 874]
[2]Bensoussan, Charlélie; Rival, Nicolas; Hanquet, Gilles; Colobert, Françoise; Reymond, Sébastien; Cossy, Janine [Tetrahedron, 2013, vol. 69, # 36, p. 7759 - 7770]
[3]Abellán Flos, Marta; García Moreno, M. Isabel; Ortiz Mellet, Carmen; García Fernández, Jose Manuel; Nierengarten, Jean-Francois; Vincent, Stéphane P. [Chemistry - A European Journal, 2016, vol. 22, # 32, p. 11450 - 11460]
[4]Glaffig, Markus; Stergiou, Natascha; Hartmann, Sebastian; Schmitt, Edgar; Kunz, Horst [ChemMedChem, 2018, vol. 13, # 1, p. 25 - 29]
[5]Xie, Yixuan; Peng, Chao; Gao, Yunyi; Liu, Xiaohong; Liu, Tianbo; Joy, Abraham [Journal of Polymer Science, Part A: Polymer Chemistry, 2017, vol. 55, # 23, p. 3908 - 3917]
  • 12
  • [ 136497-85-3 ]
  • [ 4163-65-9 ]
  • [ 168566-64-1 ]
YieldReaction ConditionsOperation in experiment
76% With boron trifluoride diethyl etherate In dichloromethane at 20℃; for 28h; Inert atmosphere;
Reference： [1]Motiei, Leila; Rahimipour, Shai; Thayer, Desiree A.; Wong, Chi-Huey; Ghadiri, M. Reza [Chemical Communications, 2009, # 25, p. 3693 - 3695]
  • 13
  • [ 22568-49-6 ]
  • [ 4163-65-9 ]
  • [ 1240042-16-3 ]
YieldReaction ConditionsOperation in experiment
66% With boron trifluoride diethyl etherate In dichloromethane at 20℃; for 72h; Molecular sieve;
Reference： [1]Location in patent: experimental part Gueyrard, David; Iori, Renato; Tatibouet, Arnaud; Rollin, Patrick [European Journal of Organic Chemistry, 2010, # 19, p. 3657 - 3664]
  • 14
  • [ 1245828-39-0 ]
  • [ 4163-65-9 ]
  • C30H32O14 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With boron trifluoride diethyl etherate In dichloromethane at 0℃; Inert atmosphere; Reflux;
Reference： [1]Location in patent: experimental part Han, Zhenfu; Pinkner, Jerome S.; Ford, Bradley; Obermann, Robert; Nolan, William; Wildman, Scott A.; Hobbs, Doug; Ellenberger, Tom; Cusumano, Corinne K.; Hultgren, Scott J.; Janetka, James W. [Journal of Medicinal Chemistry, 2010, vol. 53, # 12, p. 4779 - 4792]
  • 15
  • [ 13020-57-0 ]
  • [ 4163-65-9 ]
  • C27H28O11 [ No CAS ]
Reference： [1]Journal of Medicinal Chemistry,2010,vol. 53,p. 4779 - 4792
  • 16
  • [ 40501-41-5 ]
  • [ 4163-65-9 ]
  • [ 1259428-41-5 ]
Reference： [1]Journal of Medicinal Chemistry,2010,vol. 53,p. 4779 - 4792
  • 17
  • [ 50824-04-9 ]
  • [ 4163-65-9 ]
  • [ 1373347-10-4 ]
Reference： [1]Journal of Medicinal Chemistry,2012,vol. 55,p. 3945 - 3959
  • 18
  • [ 4163-65-9 ]
  • [ 1373346-85-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: boron trifluoride diethyl etherate / dichloromethane / 45 h / 20 °C / Inert atmosphere; Reflux 2: tetrakis(triphenylphosphine) palladium(0); caesium carbonate / 1,4-dioxane; water / 1 h / 80 °C / Inert atmosphere 3: sodium methylate / methanol / 20 °C
Reference： [1]Han, Zhenfu; Pinkner, Jerome S.; Ford, Bradley; Chorell, Erik; Crowley, Jan M.; Cusumano, Corinne K.; Campbell, Scott; Henderson, Jeffrey P.; Hultgren, Scott J.; Janetka, James W. [Journal of Medicinal Chemistry, 2012, vol. 55, # 8, p. 3945 - 3959]
  • 19
  • [ 112-27-6 ]
  • [ 4163-65-9 ]
  • [ 1033621-39-4 ]
YieldReaction ConditionsOperation in experiment
79% With boron trifluoride diethyl etherate In dichloromethane at 0 - 20℃; Inert atmosphere; 2.1 EXAMPLE 2Preparation of a Compound of Formula (II)1) SYNTHESIS OF 3,6,8-DIOXAOCTYL 2,3,4,6-TETRA-O-ACETYL-α-D-MANNO-PYRANOSIDE (Compound 1b) 60 ml (0.56 mol-8 eq.) of BF3Et2O are added dropwise, under an argon atmosphere, to a solution containing 25.7 g (0.07 mol-1 eq.) of α-D-mannose pentaacetate and 26 ml (0.21 mol-3 eq.) of triethylene glycol in 150 ml of anhydrous dichloromethane cooled to a temperature of 0° C. The reaction mixture is then left to return to ambient temperature. The mixture is kept stirring overnight, and the reaction is monitored by TLC (90/10 v/v Et2O/MeOH). Once the reaction is complete, the reaction mixture is washed successively with twice 100 ml of a saturated aqueous solution of NaHCO3, with twice 100 ml of distilled water and, finally, with 100 ml of a brine solution. The organic phase is dried over Na2SO4, filtered and evaporated under reduced pressure. The reaction crude is then purified by silica gel column chromatography, elution being carried out with 60/40 v/v PE/Et2O.Physical appearance: Yellow oil.Yield: 79%.Rf: 0.43 (90/10 v/v Et2O/MeOH).MS: (ESI+/MeOH) m/z: 503.1 [M+Na]+,(ESI-/MeOH) m/z: 479.3 [M-H]-.1H NMR (400.13 MHz, CDCl3) δ (ppm): 2.05, 2.09, 2.12, 2.13 (4 s, 12H, H2); 3.55-3.68 (m, 12H, H1', H2', H3', H4', H5', H6'); 4.05-4.11 (m, 1H, H6a); 4.17-4.24 (m, 2H, H5 and H6b); 5.18 (d, 1H, 3JH1-H2=1.8 Hz, H1); 5.20 (dd, 1H, 3JH2-H1=1.9 Hz, 3JH2-H3=3.2 Hz, H2); 5.25 (t, 1H, 3JH4-H3=3JH4-H5=9.9 Hz, H4); 5.36 (dd, 1H, 3JH3-H2=3.3 Hz, 3JH3-H4=10.1 Hz, H3).13C NMR (100.62 MHz, CDCl3) δ (ppm): 20.5 (2C), 20.6, 20.7 (4C, C2); 61.03 (1C, C6'); 62.5 (1C, C6); 66.0 (1C, C4); 66.53 (1C, C1'); 68.1 (1C, C5); 68.8 (1C, C3); 69.94 (2C, C3' and C4'); 70.1 (1C, C2); 70.44 (1C, C2'); 72.60 (1C, C5'); 91.8 (1C, C1); 169.8, 170.1, 170.2 and 170.9 (4C, C1).
66% With boron trifluoride diethyl etherate In dichloromethane at 0 - 20℃; for 36h;
Reference： [1]Current Patent Assignee: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE - US2012/269903, 2012, A1 Location in patent: Page/Page column 10
[2]Longevial, Jean-François; El Cheikh, Khaled; Aggad, Dina; Lebrun, Aurélien; van der Lee, Arie; Tielens, Frederik; Clément, Sébastien; Morère, Alain; Garcia, Marcel; Gary-Bobo, Magali; Richeter, Sébastien [Chemistry - A European Journal, 2017, vol. 23, # 56, p. 14017 - 14026]
  • 20
  • [ 145881-74-9 ]
  • [ 4163-65-9 ]
  • [ 1433192-30-3 ]
Reference： [1]Chemistry - A European Journal,2013,vol. 19,p. 5259 - 5262
  • 21
  • [ 7340-90-1 ]
  • [ 4163-65-9 ]
  • [ 1379519-57-9 ]
YieldReaction ConditionsOperation in experiment
93% With boron trifluoride diethyl etherate In dichloromethane at -78 - 20℃; Inert atmosphere; (2-Methyl-5-tert-butylphenyl) 2,3,4,6-tetra-O-acetyl-1-thia-α-D-mannopyranoside (35) To a cooled (-78 °C) solution of α-D-mannose pentaacetate (39.1 g, 100 mmol) and 2-methyl-5-tert-butylthiophenol (61 mL,300 mmol) in dry CH2Cl2 (1 L), was added BF3.Et2O(38.1 mL, 300 mmol). The reaction mixture was stirred 2 h at -78 °C, warmed to room temperature and then stirred overnight at room temperature. The reaction mixturewas quenched with aqueous saturated NaHCO3 and then extracted with CH2Cl2. The combined organic layer was washed with brine, dried (MgSO4) and concentrated under reduced pressure. The crude was purified on silica gel (30 % EtOAC in heptane) to give 35 (47.2 g, 93%) as a colourless oil. [a]26D+ 79.1 (c, 1.0, CHCl3); 1HNMR (300 MHz, CDCl3) δ: 1.29 (s, 9H), 2.02 (s, 3H), 2.05 (s, 3H), 2.07 (s,3H), 2.16 (s, 3H), 2.40 (s, 3H), 4.07 (dd, J= 12.3 Hz, J = 2.4 Hz, 1H), 4.34 (dd,J = 12.3 Hz, J = 5.0 Hz, 1H), 4.46-4.57 (m, 1H), 5.34-5.39 (m, 2H), 5.42 (d, J = 1.5 Hz), 5.51-5.54 (m, 1H), 7.14 (d,J = 8.0 Hz, 1H), 7.22 (dd, J = 8.0 Hz , J = 2.0 Hz, 1H), 7.52 (d, J= 2.0 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ:20.2, 20.5, 20.6, 20.8, 31.2, 34.4, 62.3, 66.1, 69.3, 69.8, 71.3, 85.8, 125.3,129.6, 130.1, 131.6, 136.7, 149.9, 169.6, 169.7, 169.9, 170.5; ESIHRMS Calcdfor C25H34O9S [M+Na]+: 533.1822,found 515.1820.
Reference： [1]Picard, Sébastien; Crich, David [Tetrahedron, 2013, vol. 69, # 26, p. 5501 - 5510]
  • 22
  • [ 4163-65-9 ]
  • 2,3,4,6-tetra-O-acetyl-D-mannopyranose [ No CAS ]
  • [ 13242-53-0 ]
YieldReaction ConditionsOperation in experiment
1: 67% 2: 28% With bromine In ethyl acetate at 30℃; for 19h; Irradiation; Green chemistry; 2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl bromide General procedure: Bromine (1.5 mmol, 0.08 mL) was added slowly to a magnetic stirring barand perfluorohexanes (4.0 mL) in a test tube (14 mmφ x 105 mm) with a septum and then 1-O-acetylsugar 1a (1 mmol, 392 mg) in ethyl acetate (2.0 mL) wasadded slowly, forming three layers. The test tube was stirring upon irradiationwith 15 W black light (at 352 nm, TOSHIBA EFD15BLB-T) at 30 C. The light source wasplaced away from the test tube. After 23 hours, the bromine layer disappearedand the fluorous layer recovered transparency. The ethyl acetate layer wastaken up with a pipette. Then, additional ethyl acetate (2 mL x 4) was placedon the residual FC-72 layer, followed by decanting off. The combined ethylacetate layer was washed with water (15 mL), aqueous sat. NaHCO3 (20mL), brine (20 mL) and, dried over Na2SO4, andconcentrated. Purification by chromatography on silica gel with hexane/AcOEt = 2/1gave glycosyl bromide 2a (0.91 mmol,374 mg) in 91% yield
Reference： [1]Tojino, Mami; Hirose, Yuriko; Mizuno, Mamoru [Tetrahedron Letters, 2013, vol. 54, # 52, p. 7124 - 7126]
  • 23
  • [ 423-56-3 ]
  • [ 4163-65-9 ]
  • 1-O-(1H,1H-perfluorononyl)-2,3,4,6-tetra-O-acetyl-α-D-mannopyranose [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With iron(III) chloride In dichloromethane at 20℃; 17 General procedure for glycosylation of fluoroalkyl and alkylalcohols General procedure: Perfluoroalkyl/alkyl alcohol (1 g) and peracetyl-a-mannose(1.5 equiv) were dissolved in CH2Cl2 (45 mL), to which FeCl3(3 equiv) was quickly transferred. After 3e4 h of stirring at roomtemperature the reactionwas quenched by addition of NaHCO3(aq),which caused the iron to precipitate as brick-colored Fe2(CO3)2. Thebiphasic mixture was filtered through Celite to remove the inorganicsalts, and worked up with CH2Cl2 and NaHCO3(aq). Theorganic portions were combined and dried with MgSO4. Chromatographyover silica gel (100 mL SiO2, eluted with a 15e50% ethylacetate/hexanes gradient) gave the desired products as whitefoams, or viscous oils.
Reference： [1]Razgulin, Andrew V.; Mecozzi, Sandro [Carbohydrate Research, 2015, vol. 406, p. 10 - 18]
  • 24
  • [ 423-56-3 ]
  • [ 4163-65-9 ]
  • 1-O-(1H,1H-perfluorononyl)-α-D-mannopyranose [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: iron(III) chloride / dichloromethane / 20 °C 2: methanol; sodium methylate / 20 °C
Reference： [1]Razgulin, Andrew V.; Mecozzi, Sandro [Carbohydrate Research, 2015, vol. 406, p. 10 - 18]
  • 25
  • [ 116130-33-7 ]
  • [ 4163-65-9 ]
  • [ 1312312-40-5 ]
Reference： [1]Journal of Medicinal Chemistry,2015,vol. 58,p. 2221 - 2239
[2]Journal of Medicinal Chemistry,2017,vol. 60,p. 5646 - 5662
  • 26
  • [ 699-12-7 ]
  • [ 4163-65-9 ]
  • 2-phenylthioethyl 2,3,4,6-tetra-O-acetyl-α-D-mannopyranoside [ No CAS ]
Reference： [1]Journal of the American Chemical Society,2015,vol. 137,p. 10336 - 10345
  • 27
  • [ 208827-90-1 ]
  • [ 4163-65-9 ]
  • [ 1072903-84-4 ]
YieldReaction ConditionsOperation in experiment
79% With boron trifluoride diethyl etherate In dichloromethane at 0 - 23℃;
36% With boron trifluoride diethyl etherate In dichloromethane at 0 - 20℃; for 18h; Inert atmosphere; 4.9 Protocol for step b of Scheme S1 General procedure: 5.12mmol of peracetylated glucosyl derivative 46 were dissolved in dry DCM (40mL) and cooled to 0°C under nitrogen atmosphere. Propargyl alcohol was then added (6.15mmol). Boron trifluoride etherate was finally added drop-wise (7.17mmol). The mixture was then warmed to r.t. and stirred for 18h. The reaction was quenched through the addition of potassium carbonate (1g) and subsequent stirring (30min). The salt was then filtered away and the organic phase was washed with water (50mL x2). This aqueous phase was recovered and re-extracted with DCM (100mL). The organic portions were then combined and dried over sodium sulphate. The salt was removed by filtration and the product 47 was recovered by solvent evaporation under reduced pressure. The mixture of the product and the remaining sugar was used as such for the following deprotection step. Alternatively, it could be purified by column chromatography (hexane/ethyl acetate from 7:3 to 1:1, TLC in hexane/ethyl acetate 1:1). NMR data were in good agreement with those available in the literature [43]. The same protocol was applied to the synthesis of 53 (glucose derivative) and 54-56 (mannose derivatives), using the relevant alcohol (propargyl alcohol or 3-butyn-1-ol or 2-[2-[2-(2-propyn-1-yloxy)ethoxy]ethoxy] ethanol, see Supporting Information for details).
Reference： [1]Zhang, Shaodong; Moussodia, Ralph-Olivier; Sun, Hao-Jan; Leowanawat, Pawaret; Muncan, Adam; Nusbaum, Christopher D.; Chelling, Kathleen M.; Heiney, Paul A.; Klein, Michael L.; André, Sabine; Roy, René; Gabius, Hans-J.; Percec, Virgil [Angewandte Chemie - International Edition, 2014, vol. 53, # 41, p. 10899 - 10903][Angew. Chem., 2014, vol. 126, # 41, p. 11079 - 11083,3]
[2]Zuffo; Stucchi; Campos-Salinas; Cabello-Donayre; Martínez-García; Belmonte-Reche; Pérez-Victoria; Mergny; Freccero; Morales; Doria [European Journal of Medicinal Chemistry, 2019, vol. 163, p. 54 - 66]
  • 28
  • [ 3891-07-4 ]
  • [ 4163-65-9 ]
  • 2-N-phthalimidylethyl 2,3,4,6-tetra-O-acetyl-α-D-mannopyranoside [ No CAS ]
YieldReaction ConditionsOperation in experiment
48% With boron trifluoride diethyl etherate In dichloromethane at 0 - 20℃; for 16.5h; 2.4 4.2.4. 2-N-Phthalimidylethyl 2,3,4,6-tetra-O-acetyl-α-Dmannopyranoside(13) Mannose pentaacetate (12) (273 mg, 700 μmol, 1.0 eq) and N-(2-hydroxyethyl)phthalimide (160 mg, 840 μmol, 1.2 eq) were dissolvedin dry CH2Cl2 (5.0 mL). Then, BF3·etherate (488 μL, 3.85 mmol, 5.5eq) was added dropwise at 0 °C and the solution was stirred for30 min at this temperature. After stirring for 16 h at room temperature,the solution was diluted with CH2Cl2 and the solution waspoured onto ice-cold water. The aqueous phase was extracted threetimes with CH2Cl2 and the combined organic phases were washedwith satd. aq. NaHCO3 solution, brine and water. The organic phasewas dried over MgSO4 and filtered, and the filtrate was concentratedunder reduced pressure. Purification of the crude mixture byflash chromatography (toluene/EtOAc, 3:1) gave product 13 (174 mg,334 μmol, 48%) as a colourless syrup: Rf = 0.42 (toluene/EtOAc, 1:1);1H NMR (600 MHz, CDCl3): δ 7.89-7.85 (m, 2H, Ar-H), 7.74-7.71 (m,2H, Ar-H), 5.29-5.19 (m, 3H, H-2, H-3, H-4), 4.88 (d, J1,2 = 1.4 Hz, 1H,H-1), 4.21 (dd, J5,6a = 5.5 Hz, J6a,6b = 12.2 Hz, 1H, H-6a), 4.04 (dd,J5,6b = 2.3 Hz, J6a,6b = 12.2 Hz, 1H, H-6b), 4.00-3.96 (m, 1H, OCH2CH′HN),3.94-3.88 (m, 3H, H-5, OCH2CH′HN, OCH′HCH2N), 3.79-3.75(OCH′HCH2N), 2.13, 2.10, 2.00, 1.96 (each s, each 3H, 4 OAc); 13C NMR(125 MHz, CDCl3): δ 170.8, 170.0, 169.8, 169.8, 168.2 (5 C = O), 134.2(Ar-C), 132.1 (Ar-Cquart), 123.6 (Ar-C), 97.2 (C-1), 69.5 (C-2), 69.0 (C-5), 69.0 (C-3), 66.2 (C-4), 64.7 (OCH2CH2N), 62.5 (C-6), 37.1(OCH2CH2N), 21.0, 20.9, 20.8, 20.8 (4 COCH3); ESI-MS (m/z): [M + Na]+calcd for C24H27NO12, 544.143, found, 544.143.
Reference： [1]Gloe, Tobias-Elias; Müller, Anne; Ciuk, Anna; Wrodnigg, Tanja M.; Lindhorst, Thisbe K. [Carbohydrate Research, 2016, vol. 425, p. 1 - 9]
  • 29
  • [ 2374-05-2 ]
  • [ 4163-65-9 ]
  • (2R,3R,4S,5S,6R)-2-(acetoxymethyl)-6-(4-bromo-2,6-dimethylphenoxy)-tetrahydro-2H-pyran-3,4,5-triyl triacetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
25% With boron trifluoride diethyl etherate In dichloromethane at 0 - 50℃; for 3h; 38 (2R,3R,4S,5S,6R)-2-(acetoxymethyl)-6-(4-bromo-2,6-dimethylphenoxy)-tetrahydro-2H-pyran-3,4,5-triyl triacetate To a solution of mannose pentaacetate and 4-bromo-2,6-dimethylphenol (4.6 g, 23.1 mmol) in CH2Cl2 (60 mL) was added BF3.OEt2 (47 wt%, 6 mL) drop wise at 0 °C. The resulting mixture was stirred at 50 °C for 3 hours and then cooled to room temperature and poured into ice-water (100 mL). The mixture was extracted with CH2Cl2 (100 mLx3), and the combined organic layer was washed with saturated aqueous NaHCO3 (100 mL), and brine (100 mL), then dried over anhydrous Na2SO4 and filtered. The filtrate was concentrated under vacuum and the residue was purified by silica gel chromatography, eluting with EtOAc in petroleum ether (0-50%) to afford the title compound (1.0 g, 25% yield) as a light red solid. ESI-MS [M+Na+] calcd for (C22H27BrO10Na+) 554.07, found 554.10.
Reference： [1]Current Patent Assignee: FIMBRION THERAPEUTICS INC - WO2017/165619, 2017, A1 Location in patent: Paragraph 0342; 0343
  • 30
  • [ 1104874-94-3 ]
  • [ 4163-65-9 ]
  • N-(hexanoyl)-O-α-D-mannopyranosyl-(S)-tyrosine [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: boron trifluoride diethyl etherate / dichloromethane / 0 - 20 °C 2: lithium hydroxide / tetrahydrofuran; water / 16 h / 20 °C
Reference： [1]Vudhgiri, Srikanth; Prasad; Poornachandra; Ganesh Kumar; Anjaneyulu; Sirisha; Jala, Ram Chandra Reddy [Journal of Chemical Sciences, 2017, vol. 129, # 6, p. 663 - 677]
  • 31
  • [ 1104874-94-3 ]
  • [ 4163-65-9 ]
  • C30H41NO13 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With boron trifluoride diethyl etherate In dichloromethane at 0 - 20℃; 2.8 General procedure for synthesis of N-(fatty acyl)-O-α/β-D/L-glycopyranosyl-(S)-tyrosines General procedure: To a solution of hexose penta acetate (2.56 mmol) in dichloromethane (10 mL) was added methyl N-acyl tyrosinate (3.704 mmol) and boron trifloride etherate (3.84 mmol) at 0 °C and the reaction mixture was stirred at room temperature for overnight. The reaction mixture was dissolved in CHCl3 and washed with NaHCO3 solution and water (2 × 150 mL).The organic phase was dried over sodium sulphate and concentrated to yield a liquid. The crude compound was directly used for the next step. Methyl ester (1 eq.) was dissolved in THF: H2O (7:3) and added (3 eq.) of LiOH, stirred the reaction mixture at RT for 16 h. After completion of reaction, the mixture was concentrated under vaccum to obtain a white precipitate.This white precipitate was neutralized with 2 N HCl and the reaction mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulphate. This organic layer was concentrated to yield a white solid. This solid was purified by silica gel chromatography using a gradient of chloroform/methanol (75:25, v/v) to obtain a yield (65-77%) of the title compound as a solid.
Reference： [1]Vudhgiri, Srikanth; Prasad; Poornachandra; Ganesh Kumar; Anjaneyulu; Sirisha; Jala, Ram Chandra Reddy [Journal of Chemical Sciences, 2017, vol. 129, # 6, p. 663 - 677]
  • 32
  • [ 79566-13-5 ]
  • [ 4163-65-9 ]
  • [ 28541-83-5 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: boron trifluoride diethyl etherate; pyridine / 1,2-dichloro-ethane / 5 h / 60 °C / Inert atmosphere 2: potassium hydroxide; methanol / 0.75 h / 20 °C
Reference： [1]Current Patent Assignee: GUANGDONG ACADEMY OF SCIENCES; GUANGDONG HUANKAI MICROBIAL SCI & TECHNOLOGY CO LTD - CN104926898, 2018, B
  • 33
  • [ 67580-96-5 ]
  • [ 4163-65-9 ]
  • C25H33NO12 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With boron trifluoride diethyl etherate In dichloromethane at 0 - 20℃; for 16h; Inert atmosphere; diastereoselective reaction;
Reference： [1]Pettenuzzo, Nicolò; Brustolin, Leonardo; Coltri, Elisa; Gambalunga, Alberto; Chiara, Federica; Trevisan, Andrea; Biondi, Barbara; Nardon, Chiara; Fregona, Dolores [ChemMedChem, 2019, vol. 14, # 12, p. 1162 - 1172]
  • 34
  • [ 67580-96-5 ]
  • [ 4163-65-9 ]
  • C17H25NO8 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: boron trifluoride diethyl etherate / dichloromethane / 16 h / 0 - 20 °C / Inert atmosphere 2: sodium methylate / methanol / 16 h / 20 °C / Inert atmosphere
Reference： [1]Pettenuzzo, Nicolò; Brustolin, Leonardo; Coltri, Elisa; Gambalunga, Alberto; Chiara, Federica; Trevisan, Andrea; Biondi, Barbara; Nardon, Chiara; Fregona, Dolores [ChemMedChem, 2019, vol. 14, # 12, p. 1162 - 1172]
  • 35
  • [ 4163-65-9 ]
  • [ 34213-86-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: boron trifluoride diethyl etherate / dichloromethane / 20 °C 2: sodium methylate / methanol / 20 °C 3: palladium on activated charcoal; hydrogen / methanol / 1 h / 20 °C
Multi-step reaction with 3 steps 1: boron trifluoride diethyl etherate / ethyl acetate / 20 °C 2: trifluoroacetic acid; sodium ethanolate / methanol 3: 5%-palladium/activated carbon / methanol / 1 h
Reference： [1]Current Patent Assignee: HARBIN MEDICAL UNIVERSITY - CN111249234, 2020, A
[2]Current Patent Assignee: HARBIN MEDICAL UNIVERSITY - CN111249235, 2020, A
  • 36
  • [ 7646-67-5 ]
  • [ 4163-65-9 ]
  • [ 1254975-44-4 ]
YieldReaction ConditionsOperation in experiment
52% With boron trifluoride diethyl etherate In dichloromethane at 0 - 20℃; for 48h; 4.2 1.2 2'-acrylamidoethyl-2,3,4,6-tetra-O-acetyl-α-D-mannopyranoside (AcManEAm) The synthesis of 2'-acrylamidoethyl-2,3,4,6-tetra-O-acetyl-α-D-mannopyranoside (AcManEAm) is very similar to the synthesis of AcGalEAM. 10,0 g (78,2 mmol) N-(2-Hydroxyethyl)-acrylamid and 33,4 g (85,5 mmol) 1,2,3,4,6-Penta-O-acetyl-α-D-mannopyranoside are dissolved in 700 ml of dichloromethane, cooled down to 0 °C and flushed with nitrogen for 15 min inside a 1000 ml three-neck-flask. After the slow addition of 42 ml (331,4 mmol) boron trifluoride ethyl etherate, the reaction solution is stirred at room temperature for 48 h. The organic layer is washed with with icewater, 3 times with saturated sodium hydrogen carbonate solution and with ultrapure water. After drying the orangic layer over magnesium sulfate, dichloromethane is removed by distillation under vacuum and reduced pressure. The synthesized AcManEAm is purified by column chromatography (Gradient: ethyl acetate/n-hexane 1:1 to pure n-hexane). The yield of the remaining product is 52 % (18,0 g, 40 mmol).
Reference： [1]Jäck, Nicholas; Müller, Janita; Paul, Tanja J.; Saatkamp, Torben H.; Schmidt, Stephan; Schröer, Fabian; Strzelczyk, Alexander K.; Wilms, Dimitri [Molecules, 2021, vol. 26, # 2]

Tags: 4163-65-9 synthesis path| 4163-65-9 SDS| 4163-65-9 COA| 4163-65-9 purity| 4163-65-9 application| 4163-65-9 NMR| 4163-65-9 COA| 4163-65-9 structure

Same Skeleton Products
Related Products
Categories
Chemistry
Heterocyclic Building Blocks
Tetrahydropyrans
2-tetrahydropyranyl
Chemistry
Chemical Biology
Glycoscience
Historical Records