반응 #511542

반응 방정식

tert-butyllithium

HCl

vinyl boronic acid

Compound 5b

2-Bromo-5-fluoro-[1-(methoxymethoxy)methyl]benzene

→

11

수율 30.0%

1,3-Dihydro-5-fluoro-1-vinyl-2,1-benzoxaborole

수율 30.0%

용매

pentane

Water

THF

반응 조건

후처리

1. 1
   workup.STIRRINGThe mixture was stirred at −78° C. for 1 h
2. 2
   온도was warmed up to room temperature
3. 3
   workup.STIRRINGstirred overnight
4. 4
   workup.STIRRINGwas stirred at room temperature for 4 h
5. 5
   기타THF was removed under reduced pressure
6. 6
   추출The residue was extracted with ethyl ether
7. 7
   세척washed with brine
8. 8
   건조dried over magnesium sulfate
9. 9
   농축concentrated under reduced pressure
10. 10
    기타The crude product was purified by flash column chromatography (9:1 hexane/ethyl acetate)

실험 절차

Compound 5b (2.0 g, 8.0 mmol) in THF (30 mL) was cooled to −78° C. and tert-butyllithium (9.9 mL, 16.8 mmol) as 1.7 M solution in pentane was added slowly. After stirring at −78° C. for 30 min, dibutyl ester of vinyl boronic acid was added dropwise. The mixture was stirred at −78° C. for 1 h, then was warmed up to room temperature and stirred overnight. Concentrated HCl (4 mL) was added and was stirred at room temperature for 4 h. Water (10 mL) was added and THF was removed under reduced pressure. The residue was extracted with ethyl ether, washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure. The crude product was purified by flash column chromatography (9:1 hexane/ethyl acetate) to give 11 (383 mg, 30%) as a yellowish oil; 1H NMR (300 MHz, DMSO-d6) δ (ppm) 5.27 (s, 2H), 6.25 (t, J=8.5 Hz, 1H), 6.50 (d, J=9.4 Hz, 2H), 7.06-7.15 (m, 2H), 7.89 (dd, J=5.6, 7.9 Hz, 1H); ESI-MS m/z (M+H)+; HPLC purity: 98.7%; Anal. (C9H8BFO 0.1H2O)C, H.

출처