Reaction #710553

Reaction equation

tert-butyl 3-(tert-butyldimethylsilyloxy)-2-oxopropylcarbamate

fluoromethyl(triphenyl)-phosphonium tetrafluoroborate

sodium bis(trimethylsilyl)amide

→

tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-3-fluoroallylcarbamate

Solvents

THF

THF

Conditions

Workup

1. 1
   workup.WAITThe resulting deep orange solution was left
2. 2
   workup.STIRRINGto stir at this temperature for 15 min
3. 3
   workup.ADDITIONAfter complete addition
4. 4
   workup.STIRRINGstirring
5. 5
   OtherThe reaction was quenched by addition of water (5 mL)
6. 6
   Concentrationthe reaction mixture was concentrated in vacuo
7. 7
   OtherThe residue was partitioned between water (100 mL) and diethyl ether (100 mL)
8. 8
   Extractionthe aqueous layer was extracted with further diethyl ether (2×100 ml)
9. 9
   DryingThe combined organics were dried over Na2SO4
10. 10
    Concentrationconcentrated under reduced pressure
11. 11
    OtherThe crude residue was purified over silica gel eluting with n-hexane

Procedure

To a vigorously stirring suspension of fluoromethyl(triphenyl)-phosphonium tetrafluoroborate (18.9 g, 49.4 mmol) in dry THF (190 mL) at −20° C. under N2 was added sodium bis(trimethylsilyl)amide (1.0 M in THF; 49.4 mL, 49.4 mmol) slowly over 10 min. The resulting deep orange solution was left to stir at this temperature for 15 min. A solution of tert-butyl 3-(tert-butyldimethylsilyloxy)-2-oxopropylcarbamate (10.0 g, 33.0 mmol) in THF (10 mL) was then added slowly over 10 min. After complete addition, stirring was continued for a further 1 h during which time the reaction was allowed to warm slowly to room temperature. The reaction was quenched by addition of water (5 mL) and the reaction mixture was concentrated in vacuo. The residue was partitioned between water (100 mL) and diethyl ether (100 mL) and the aqueous layer was extracted with further diethyl ether (2×100 ml). The combined organics were dried over Na2SO4 and concentrated under reduced pressure. The crude residue was purified over silica gel eluting with n-hexane followed by 6% ethylacetate in n-hexane to give tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-3-fluoroallylcarbamate as a mixture of E/Z double-bond isomers (E/Z=1:1; 9.9 g; 94%). The isomers were not separated at this stage.

Source