反応 #1951035

反応方程式

MeOH CHCl3

3-Formyl-2,5,6-trichloro-1-[3,5-di-O-(p-toluoyl)-2-deoxy-β-D-ribofuranosyl]indole

sodium methoxide

→

4.114

収率 69.0%

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

収率 69.0%

溶媒

MeOH

MeOH

反応条件

後処理

1. 1
   その他The solvent was then removed under vacuum
2. 2
   抽出extracted with EtOAc (2×100 mL)
3. 3
   洗浄The combined organic extracts were washed with brine (25 mL)
4. 4
   乾燥dried over MgSO4
5. 5
   ろ過filtered
6. 6
   その他evaporated
7. 7
   その他to yield a damp solid
8. 8
   workup.ADDITIONFractions containing product
9. 9
   その他evaporated
10. 10
    その他to yield a white solid
11. 11
    その他The solid was recrystallized
12. 12
    温度from warm MeOH

実験手順

3-Formyl-2,5,6-trichloro-1-[3,5-di-O-(p-toluoyl)-2-deoxy-β-D-ribofuranosyl]indole (4.113, 198 mg, 0.33 mmol) was suspended in dry MeOH (10 mL) to which was added sodium methoxide (75 mg, 1.4 mmol). The suspension was stirred at room temperature for 16 h, after which time the solution clarified. The solvent was then removed under vacuum, and the residue was suspended in water (50 mL), and extracted with EtOAc (2×100 mL). The combined organic extracts were washed with brine (25 mL), dried over MgSO4, filtered and evaporated to yield a damp solid. The crude material was dissolved in MeOH (1 mL) and subjected to column chromatography (40×350 mm) on silica gel with 10% MeOH/CHCl3. Fractions containing product were pooled and evaporated to yield a white solid. The solid was recrystallized from warm MeOH to yield 82 mg (68%) of 4.114 as a white crystalline solid: mp 186-187° C.; Rf0.3 (10% MeOH/CHCl3); 1H-NMR (500 MHz, DMSO-d6): δ 10.21 (s, 1H), 8.29 (s, 1H), 8.22 (s, 1H), 6.32 (dd, 1H), 5.37 (b, 1H, D2O exch.), 5.15 (b, 1H, D2O exch.), 4.43 (s, 3H), 4.41 (m, 1H), 3.83 (d, 1H), 3.68 (m, 2H), 2.53 (m, 1H), 2.11 (m, 1H). 13C-NMR (125 MHz, DMSO-d6): δ 183.22, 159.16, 129.40, 125.04, 124.73, 124.66, 121.11, 114.24, 100.02, 87.29, 82.99, 70.07, 64.16, 61.03, 38.43. HRMS (EI) m/z calcd. for C15H15Cl2NO5 359.0327, found 359.0320. Anal calcd for C15H15Cl2NO5.½H2O: C, 48.80; H, 4.37; N, 3.79. Found: C, 48.48; H, 4.61; N, 3.61.

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