Реакция #710553

Уравнение реакции

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

fluoromethyl(triphenyl)-phosphonium tetrafluoroborate

sodium bis(trimethylsilyl)amide

→

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

Растворители

THF

THF

Условия реакции

Обработка

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
   ДругоеThe reaction was quenched by addition of water (5 mL)
6. 6
   Концентрированиеthe reaction mixture was concentrated in vacuo
7. 7
   ДругоеThe residue was partitioned between water (100 mL) and diethyl ether (100 mL)
8. 8
   Экстракцияthe aqueous layer was extracted with further diethyl ether (2×100 ml)
9. 9
   СушкаThe combined organics were dried over Na2SO4
10. 10
    Концентрированиеconcentrated under reduced pressure
11. 11
    ДругоеThe crude residue was purified over silica gel eluting with n-hexane

Методика

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.

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