Toluene → (3R,4S,5R,6R)-3,4,5-Tris-trimethylsilanyloxy-6-trimethylsilanyloxymethyl-tetrahydro-pyran-2-on

HRID 628751Notes

Reaction equation

HRID 628751 reaction equation
[OH:1][C@@H:2]1[C@@H:7]([OH:8])[C@H:6]([OH:9])[C@@H:5]([CH2:10][OH:11])[O:4][C:3]1=[O:12].CN1CCOCC1.[Cl-].[CH3:21][SiH:22]([CH3:24])[CH3:23].C1(C)C=CC=CC=1>O1CCCC1.O>[CH3:21][Si:22]([CH3:24])([CH3:23])[O:1][C@@H:2]1[C@@H:7]([O:8][Si:22]([CH3:24])([CH3:23])[CH3:21])[C@H:6]([O:9][Si:22]([CH3:24])([CH3:23])[CH3:21])[C@@H:5]([CH2:10][O:11][Si:22]([CH3:24])([CH3:23])[CH3:21])[O:4][C:3]1=[O:12]

Participants

7

Reactant 4

HCID 1140TolueneHCID 7027delta-GluconolactoneHCID 79724-MethylmorpholineHCID 131723440Tmsci

Product 1

HCID 10994280(3R,4S,5R,6R)-3,4,5-Tris-trimethylsilanyloxy-6-trimethylsilanyloxymethyl-tetrahydro-pyran-2-onYield 100%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
35 °C

Procedure

(3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-one (85 g, 0.47 mol) was suspended in THF (tetrahydrofuran) (932 mL). To the resulting mixture was added N-methylmorpholine (405 mL, 4.78 mol). Then the resulting mixture was cooled to −5° C. under a nitrogen protection, and TMSCI (trimethylsilane chloride) (360 mL, 4.78 mol) was added dropwise thereto. After the completion of dropwise addition, the resulting mixture was stirred at room temperature for 1 h and at 35° C. for 5 hr. Then the mixture was stirred overnight while the temperature was maintained at 25° C. TLC indicated the completion of reaction. To the reaction mixture was added toluene (200 mL) and added dropwise water (1 L) in an ice-water bath. The organic phase was collected, washed with sodium dihydrogen phosphate for one time, with water for one time, and with a saturated sodium chloride solution for one time, dried and concentrated to produce 218 g of a product in a yield of 100%.

Workup

  1. additionwas added dropwise
  2. additionAfter the completion of dropwise addition
  3. stirringThen the mixture was stirred overnight while the temperature
  4. temperaturewas maintained at 25° C
  5. customthe completion of reaction
  6. customThe organic phase was collected
  7. washwashed with sodium dihydrogen phosphate for one time, with water for one time
  8. dry with materialwith a saturated sodium chloride solution for one time, dried
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-643ed2b41d7941a494ab00bd5019fd6e
Source dataset
uspto-grants-2016_04
Patent number
US09315438B2

Reaction notes

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