反応 #1951037

反応方程式

5,6-Dichloro-2-bromo-3-formyl-1-(5-O-acetyl-β-D-ribofuranosyl)indole

sodium methoxide

MeOH H2O

→

4.137

収率 47.0%

5,6-Dichloro-2-bromo-3-formyl-1-(β-D-ribofuranosyl)indole

収率 47.0%

溶媒

MeOH

MeOH

反応条件

後処理

1. 1
   その他was consumed (TLC)
2. 2
   workup.ADDITIONWater (30 mL) was added
3. 3
   その他the solution evaporated until the MeOH
4. 4
   その他was completely removed
5. 5
   抽出The residual aqueous suspension was extracted with EtOAc (3×30 mL)
6. 6
   洗浄the combined organic extracts washed with brine (20 mL)
7. 7
   乾燥dried over MgSO4
8. 8
   ろ過filtered
9. 9
   その他evaporated
10. 10
    その他to yield a white solid
11. 11
    workup.ADDITIONFractions containing product
12. 12
    その他evaporated
13. 13
    その他to yield a white solid which
14. 14
    その他was recrystallized from MeOH and H2O

実験手順

5,6-Dichloro-2-bromo-3-formyl-1-(5-O-acetyl-β-D-ribofuranosyl)indole (4.136, 101 mg, 0.22 mmol) was dissolved in dry MeOH (10 mL) to which was added sodium methoxide (25 mg, 0.46 mmol). The solution was stirred at room temperature for 15 min, until the starting material was consumed (TLC). Water (30 mL) was added and the solution evaporated until the MeOH was completely removed. The residual aqueous suspension was extracted with EtOAc (3×30 mL) and the combined organic extracts washed with brine (20 mL), dried over MgSO4, filtered and evaporated to yield a white solid. The solid was dissolved in MeOH (1 mL) and subjected to column chromatography (40×350 mm) on C18-reverse phase silica gel with 75% MeOH/H2O. Fractions containing product were pooled and evaporated to yield a white solid which was recrystallized from MeOH and H2O to yield 43 mg (47%) of 4.137 as a pale tan powder: mp 210-211° C.; Rf0.2 (10% MeOH/CHCl3); 1H-NMR (500 MHz, DMSO-d6): δ 9.95 (s, 1H), 8.69 (s, 1H), 8.28 (s, 1H), 6.06 (d, 1H), 5.49-5.43 (m, 2H, D2O exch.), 5.31 (d, 1H, D2O exch.), 4.44 (q, 1H), 4.18 (m, 1H), 4.04 (d, 1H), 3.77-3.71 (m, 2H). 13C-NMR (125 MHz, DMSO-d6): δ 185.53, 134.05, 128.85, 126.58, 126.47, 125.31, 120.56, 116.00, 114.68, 90.27, 86.55, 71.69, 69.62, 60.98. HRMS (EI) m/z calcd. for C14H12BrCl2NO5 422.9276, found 422.9271. Anal calcd for C14H12BrCl2NO5: C, 39.56; H, 2.85; N, 3.30. Found: C, 39.77; H, 3.03; N, 3.32.

出典