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

HRID 1055496Notes

Reaction equation

HRID 1055496 reaction equation
CN1CCOCC1.[OH:8][C@@H:9]1[C@@H:14]([OH:15])[C@H:13]([OH:16])[C@@H:12]([CH2:17][OH:18])[O:11][C:10]1=[O:19].[CH3:20][Si:21]([CH3:24])([CH3:23])Cl>O1CCCC1>[CH3:20][Si:21]([CH3:24])([CH3:23])[O:8][C@@H:9]1[C@@H:14]([O:15][Si:21]([CH3:24])([CH3:23])[CH3:20])[C@H:13]([O:16][Si:21]([CH3:24])([CH3:23])[CH3:20])[C@@H:12]([CH2:17][O:18][Si:21]([CH3:24])([CH3:23])[CH3:20])[O:11][C:10]1=[O:19]

Participants

5

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 7027delta-GluconolactoneHCID 79724-Methylmorpholine

Product 1

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

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of N-methylmorpholine (246.8 mL, 2.24 mol) and (3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydropyran-2-one 1a (50 g, 0.28 mol, bought from Aladdin) in anhydrous tetrahydrofuran (500 mL) was added dropwise trimethylchlorosilane (213 mL, 1.68 mol) over a period of 2 hours. The mixture was stirred at room temperature (rt) for 8 hours and quenched with 1 L of water. The resulting mixture was partitioned. The organic layer was washed with saturated aqueous dipotassium hydrogen phosphate (100 mL×8.3) and saturated aqueous sodium chloride (100 mL×8.3), dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was purified by silica gel chromatography eluted with PE/EtOAc(v/v)=40/1 to give the title compound 1b as colorless oil (125.2 g, 100%). The compound was characterized by the following spectroscopic data: 1H NMR (400 MHz, CDCl3) δ(ppm): 4.17 (m, 1H), 3.99 (d, 1H), 3.89 (t, 1H), 3.81 (m, 3H), 0.18 (s, 9H), 0.17 (s, 9H), 0.15 (s, 9H), 0.11 (s, 9H).

Workup

  1. customquenched with 1 L of water
  2. customThe resulting mixture was partitioned
  3. washThe organic layer was washed with saturated aqueous dipotassium hydrogen phosphate (100 mL×8.3) and saturated aqueous sodium chloride (100 mL×8.3)
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by silica gel chromatography
  7. washeluted with PE/EtOAc(v/v)=40/1

Sources & evidence

ORD record
ord-ad20ee15ec5c40cfa63a01c145537afb
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

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