Tetrabutylammonium Fluoride → tert-Butyl (E)-(3-fluoro-2-(hydroxymethyl)allyl)carbamate

To a stirring solution of tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-3-fluoroallylcarbamate (E/Z=1:1; 12.0 g, 37.6 mmol) in THF (30 mL) at room temperature was added TBAF (1:0 M in THF; 45.1 mL, 45.1 mmol). The resulting solution was left to stir for 30 min. The reaction mixture was partitioned between water (70 mL) and ethyl acetate (50 mL). The aqueous layer was extracted with ethyl acetate (50 mL) and the combined organics were washed with saturated aqueous NH4Cl (70 mL) followed by brine (70 mL). After drying over Na2SO4, the organics were concentrated in vacuo. Purification of the crude material over silica gel eluting with 20% ethyl acetate and 5% THF in n-hexane gave (Z)-tert-butyl 3-fluoro-2-(hydroxymethyl)-allylcarbamate (0.5 g, 6.5%), (E)-tert-butyl 3-fluoro-2-(hydroxymethyl)allylcarbamate (1.2 g, 15.6%) and a mixture of the E/Z isomers (5.5 g, 71.4%).

1. waitThe resulting solution was left
2. customThe reaction mixture was partitioned between water (70 mL) and ethyl acetate (50 mL)
3. extractionThe aqueous layer was extracted with ethyl acetate (50 mL)
4. washthe combined organics were washed with saturated aqueous NH4Cl (70 mL)
5. dry with materialAfter drying over Na2SO4
6. concentrationthe organics were concentrated in vacuo
7. customPurification of the crude material over silica gel eluting with 20% ethyl acetate and 5% THF in n-hexane

ORD record

ord-53f8f9e908f141e680a9dbca705e9e8a

Source dataset

uspto-grants-2016_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09302986B2