[(2R,3S,4R,5R)-5-(3-acetyl-2,5,6-trichloro-indol-1-yl)-3,4-dihydroxy-tetrahydrofuran-2-yl]methyl acetate → 1-[2,5,6-trichloro-1-[(2R,3R,4S,5R)-3,4-dihydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl]indol-3-yl]ethanone

HRID 219536Notes

Reaction equation

HRID 219536 reaction equation
[Cl:1][C:2]1[N:3]([C@@H:16]2[O:22][C@H:21]([CH2:23][O:24]C(=O)C)[C@@H:19]([OH:20])[C@H:17]2[OH:18])[C:4]2[C:9]([C:10]=1[C:11](=[O:13])[CH3:12])=[CH:8][C:7]([Cl:14])=[C:6]([Cl:15])[CH:5]=2.C[O-].[Na+]>CO>[Cl:1][C:2]1[N:3]([C@@H:16]2[O:22][C@H:21]([CH2:23][OH:24])[C@@H:19]([OH:20])[C@H:17]2[OH:18])[C:4]2[C:9]([C:10]=1[C:11](=[O:13])[CH3:12])=[CH:8][C:7]([Cl:14])=[C:6]([Cl:15])[CH:5]=2

Participants

4

Reactant 2

HCID 3012588[(2R,3S,4R,5R)-5-(3-acetyl-2,5,6-trichloro-indol-1-yl)-3,4-dihydroxy-tetrahydrofuran-2-yl]methyl acetateHCID 10942334Sodium Methoxide

Product 1

HCID 30125661-[2,5,6-trichloro-1-[(2R,3R,4S,5R)-3,4-dihydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl]indol-3-yl]ethanoneYield 81.3%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

2,5,6-Trichloro-3-acetyl-1-(5-O-acetyl-β-D-ribofuranosyl)indole (4.43, 232 mg, 0.53 mmol) was dissolved in dry MeOH (20 mL) to which was added sodium methoxide (35 mg, 0.65 mmol). The solution was stirred at room temperature for 45 min, and the solvent was then removed under vacuum. The residue was suspended in 10% aqueous NaHCO3 (50 mL) and the suspension extracted with EtOAc (2×50 mL). The combined organic extracts were dried over MgSO4, filtered and evaporated to yield a white solid. The solid was recrystallized from boiling EtOAc/hexane to yield 170 mg (81%) of 4.46 as a white crystalline solid: mp 249-250 C; Rf 0.4 (10% MeOH/CHCl3); 1H-NMR (500 MHz, DMSO-d6): δ 8.63 (s, 1H), 8.41 (s, 1H), 6.07 (d, 1H), 5.45-5.42 (m, 2H, D2O exch.), 5.30 (d, 1H, D2O exch.), 4.44 (q, 1H), 4.17 (d, 1H), 4.03 (d, 1H), 3.75 (b, 2H), 2.63 (s, 3H). 13C-NMR (125 MHz, DMSO-d6): δ 192.17, 133.10, 132.38, 126.21, 126.00, 125.73, 122.00, 115.44, 112.99, 88.97, 86.39, 71.63, 69.54, 60.97, 30.72. HRMS (ES) m/z calcd. for C15H14Cl3NO5 Na 415.9835. found 415.9843. Anal calcd for C15H14Cl3NO5: C, 45.65; H, 3.58; N, 3.55. Found: C, 45.75; H, 3.78; N, 3.61.

Workup

  1. customthe solvent was then removed under vacuum
  2. extractionthe suspension extracted with EtOAc (2×50 mL)
  3. dry with materialThe combined organic extracts were dried over MgSO4
  4. filtrationfiltered
  5. customevaporated
  6. customto yield a white solid
  7. customThe solid was recrystallized

Sources & evidence

ORD record
ord-4094036c68464ecd99059fac2c69363b
Source dataset
uspto-grants-2012_06
Patent number
US08202844B2

Reaction notes

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