反応 #580328

反応方程式

4

5-Bromo-1,3-dihydro-pyrrolo[2,3-b]pyridin-2-one

3-fluorophenylboronic acid

LiCl

Na2CO3

→

brown semisolid

収率 150.6%

5-(3-Fluoro-phenyl)-1,3-dihydro-pyrrolo[2,3-b]pyridin-2-one

収率 150.6%

溶媒

EtOH

toluene

反応条件

後処理

1. 1
   温度was refluxed overnight
2. 2
   温度reflux
3. 3
   温度The mixture was cooled
4. 4
   その他the organic layer was separated
5. 5
   洗浄washed with brine (100 mL)
6. 6
   抽出extracted with AcOEt (4×400 mL)
7. 7
   洗浄Combined extracts were washed with brine
8. 8
   workup.ADDITIONadded to the organic layer
9. 9
   乾燥dried with MgSO4
10. 10
    濃縮The solution was concentrated to dryness in vacuum

実験手順

A mixture of 4 (16.63 g, 78.5 mmol), 3-fluorophenylboronic acid (16.47 g, 117.7 mmol), Pd(PPh3)2Cl2 (2.73 g, 6.60 mmol), LiCl (9.95 g, 0.23 mol), 1.0 M aqueous Na2CO3 solution (196 mL, 0.196 mol) in EtOH (470 mL)—toluene (470 mL) was refluxed overnight. More Pd(PPh3)2Cl2 (1.30 g, 3.14 mmol) was added and reflux was continued for 24 h. The mixture was cooled, and the organic layer was separated and washed with brine (100 mL). The washings were combined with the aqueous layer and extracted with AcOEt (4×400 mL). Combined extracts were washed with brine, added to the organic layer and dried with MgSO4. The solution was concentrated to dryness in vacuum to give 26.98 g of brown semisolid, which was triturated with ether:hexane=1:1 (2×500 mL). The residue was dried in vacuum to afford 5 (16.85 g, 94%) as tan solid, which was used in the next step without further purification. 1H NMR (400 MHz, CDCl3) δ 3.66 (s, 2H), 7.08 (dddd, J=8.4, 8.2, 2.4, 0.9 Hz, 1H), 7.22 (ddd, J=10.0, 2.4, 1.7 Hz, 1H), 7.30 (ddd, J=8.1, 1.7, 0.9 Hz, 1H), 7.43 (ddd, J=8.2, 8.1, 6.0 Hz, 1H), 7.69 (s, 1H), 8.36 (d, J=2.1 Hz, 1H), 8.98 (bs, 1H).

出典