Reaction #87485

Reaction equation

1-bromomethyl-4-methoxy-benzene

((3S,4S,5R)-6-allyloxy-3,4,5-tris-benzyloxy-2-hydroxymethyl-tetrahydro-pyran-2-yl)-methanol

Sodium hydride

→

product

Yield 52.0%

(3S,4S,5R)-6-allyloxy-3,4,5-tris-benzyloxy-2,2-bis-(4-methoxy-benzyloxymethyl)-tetrahydro-pyran

Yield 52.0%

Solvents

N,N-dimethylformamide

Conditions

Workup

1. 1
   TemperatureThe reaction was then heated to 60° C. overnight
2. 2
   TemperatureThe mixture was cooled down to room temperature
3. 3
   Otherthe reaction was quenched with water
4. 4
   Extractionextracted with ethyl acetate (2 times)
5. 5
   WashThe combined organic layers were washed with water, brine
6. 6
   Dryingdried over sodium sulfate
7. 7
   Filtrationfiltered
8. 8
   Concentrationconcentrated under reduced pressure
9. 9
   OtherThe reaction was then chromatographed over silica gel (
10. 10
    Washeluting with a gradient of 0 to 80% ethyl acetate in heptane)

Procedure

The starting diol [((3S,4S,5R)-6-allyloxy-3,4,5-tris-benzyloxy-2-hydroxymethyl-tetrahydro-pyran-2-yl)-methanol (I-1b: 10 g, 19.208 mmol) was dissolved in N,N-dimethylformamide (70 mL) and cooled to 0° C. Sodium hydride (60% dispersion in mineral oil, 1.69 g, 42.3 mmol) was added and the reaction was allowed to stir at 0° C. for 1 hour before the addition of 1-bromomethyl-4-methoxy-benzene (5.96 mL, 40.3 mmol). The reaction was then heated to 60° C. overnight. The mixture was cooled down to room temperature and the reaction was quenched with water and extracted with ethyl acetate (2 times). The combined organic layers were washed with water, brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The reaction was then chromatographed over silica gel (eluting with a gradient of 0 to 80% ethyl acetate in heptane) yielding 7.55 g (52% yield) of product (I-1c). MS 778.8 (M+NH4+; positive mode).

Source