Sodium Bicarbonate → allyl 3,4,6-tri-O-benzyl-beta-D-glucopyranoside

HRID 64248

Reaction equation

HRID 64248 reaction equation
[CH2:1]([O:8][C@H:9]1[C@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@@H:13]([CH2:23][O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[O:12][CH:11]=[CH:10]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:32]([O-:35])(O)=O.[Na+].[OH:37]OS([O-])=O.[K+].C(Cl)Cl.[CH3:46][C:47](C)=O>O>[CH2:1]([O:8][C@H:9]1[C@H:14]([O:15][CH2:16][C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[C@@H:13]([CH2:23][O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[O:12][C@@H:11]([O:35][CH2:32][CH:46]=[CH2:47])[C@@H:10]1[OH:37])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 516892Sodium BicarbonateHCID 11742644Tri-O-benzyl-D-glucalHCID 21584124Propan-2-one--dichloromethane (1/1)HCID 23707502Potassium hydroxy sulfite

Product 1

HCID 11027377allyl 3,4,6-tri-O-benzyl-beta-D-glucopyranosideYield 50%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

3,4,6-tri-O-benzyl-D-glucal (7.2 g, 17.3 mmol) in CH2Cl2/acetone (2:1, 105 mL) and a saturated solution of NaHCO3 (100 mL) was added. The mixture was stirred vigorously while a solution of Oxone (21.2 g, 34.6 mmol) in water (150 mL) was added dropwise over 30 minutes. After 1.5 hours of vigorous stirring the layers were separated, and the aqueous layer was extracted with CH2Cl2 (2×150 mL). The organic solutions were combined, dried over MgSO4, filtered and concentrated. The residue was co-evaporated with toluene (3×10 mL), dissolved in allyl alcohol (25 mL) and stirred at room temperature overnight. The reaction mixture was purified on a silica gel column (80 g) using an ISCO automated chromatography system, eluting with a 0→60% gradient of ethyl acetate in heptane, to give allyl 3,4,6-tri-O-benzyl-β-D-glucopyranoside (4.2 g, 50%).

Workup

  1. additionwas added dropwise over 30 minutes
  2. customwere separated
  3. extractionthe aqueous layer was extracted with CH2Cl2 (2×150 mL)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. dissolutiondissolved in allyl alcohol (25 mL)
  8. stirringstirred at room temperature overnight
  9. customThe reaction mixture was purified on a silica gel column (80 g)
  10. washeluting with a 0→60% gradient of ethyl acetate in heptane

Sources & evidence

ORD record
ord-bba88a93227143cebe8f3aba0f22b6a6
Source dataset
uspto-grants-2016_09
Patent number
US09447133B2

Linked notes

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