반응 #9652

반응 방정식

methyl 4-(4-bromophenyl)-2,2-dimethyl-4-oxobutanoate

bis(pinacolato)diboron

potassium acetate

5-chloro-2-nitroanisole

cesium carbonate

→

methyl 4-(3′-methoxy4′-nitro-1,1′-biphenyl-4-yl)-2,2-dimethyl-4-oxobutanoate

수율 48.2%

용매

N,N-dimethylformamide

water

반응 조건

후처리

1. 1
   기타was degassed
2. 2
   기타by bubbling a flow of argon for 30 minutes
3. 3
   온도After the mixture was cooled to rt
4. 4
   온도the reaction mixture was heated at 80° C. for 16 h
5. 5
   온도The mixture was then cooled to rt
6. 6
   추출The aqueous layer was extracted with ethyl acetate
7. 7
   건조the combined organic phases were dried over anhydrous sodium sulfate
8. 8
   기타Solvent was removed under reduced pressure
9. 9
   기타the residue was purified by flash chromatography (Biotage Flash 40M, 1:3 ethyl acetate/hexane)

실험 절차

A suspension of methyl 4-(4-bromophenyl)-2,2-dimethyl-4-oxobutanoate (200 mg, 0.67 mmol), bis(pinacolato)diboron (170 mg, 0.67 mmol), potassium acetate (197 mg, 2.01 mmol), and palladium acetate (5 mg, 0.02 mmol) in N,N-dimethylformamide (4.0 mL) was degassed by bubbling a flow of argon for 30 minutes. The reaction mixture was then heated at 80° C. for 3 h. After the mixture was cooled to rt, 5-chloro-2-nitroanisole (125 mg, 0.67 mmol), tetrakis(triphenyl-phosphine)palladium(0) (23 mg, 0.02 mmol), and cesium carbonate (327 mg, 1.0 mmol) were added and the reaction mixture was heated at 80° C. for 16 h. The mixture was then cooled to rt, and water was added. The aqueous layer was extracted with ethyl acetate and the combined organic phases were dried over anhydrous sodium sulfate. Solvent was removed under reduced pressure and the residue was purified by flash chromatography (Biotage Flash 40M, 1:3 ethyl acetate/hexane) to afford methyl 4-(3′-methoxy4′-nitro-1,1′-biphenyl-4-yl)-2,2-dimethyl-4-oxobutanoate (120 mg, 48%). LC-MS ret. time 3.38 min, m/z 371.8 (MH+); 1H NMR (300 MHz, CDCl3) δ 1.19 (s, 6H), 3.36 (s, 2H), 3.51 (s, 3H), 4.02 (s, 3H), 7.21–7.24 (m, 2H), 7.64–7.69 (m, 2H), 7.93 (d, 1H), 8.00–8.04 (m, 2H).

출처