4-Nitrobenzoic Acid → HCID 10994638, compound

HRID 1108481Notes

Reaction equation

HRID 1108481 reaction equation
[C:1]([O:4][CH2:5][C@H:6]1[C:14]2[C:9](=[CH:10][C:11]([O:22][CH2:23][C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)=[C:12]([NH:15][CH:16]([C:18]([O:20][CH3:21])=[O:19])[CH3:17])[CH:13]=2)[N:8]([C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])[CH2:7]1)(=[O:3])[CH3:2].[N+](C1C=CC(C(O)=O)=CC=1)([O-])=O>CC(N(C)C)=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[O-2].[O-2].[Mn+4]>[C:1]([O:4][CH2:5][C@H:6]1[C:14]2=[C:13]3[C:12](=[C:11]([O:22][CH2:23][C:24]4[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=4)[CH:10]=[C:9]2[N:8]([C:30]([O:32][C:33]([CH3:35])([CH3:34])[CH3:36])=[O:31])[CH2:7]1)[NH:15][C:16]([C:18]([O:20][CH3:21])=[O:19])=[CH:17]3)(=[O:3])[CH3:2]

Participants

6

Reactant 2

HCID 61084-Nitrobenzoic AcidHCID 11027464HCID 11027464, compound

Product 1

HCID 10994638HCID 10994638, compoundYield 23.2%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 178418406HCID 178418406, compoundCatalystHCID 31374DimethylacetamideSolvent

Procedure

5.82 g (11.7 mmole) of (3S)-3-acetoxymethyl-5-[1-(methoxycarbonyl)ethyl]amino-6-benzyloxy-1-t-butoxycarbonylindoline, 5.24 g (23.4 mmole) of palladium acetate, 1.52 g (17.5 mmole) of manganese dioxide, and 1.95 g (11.7 mmole) of 4-nitrobenzoic acid were heated in 500 ml of dimethylacetamide at 90° C. for 18 hours. The reaction mixture was concentrated, ethyl acetate was added to the obtained residue, insoluble matter was removed by filtration, and the obtained filtrate was concentrated to give a residue. The residue was then purified by silica gel column chromatography with changing an eluate from benzene:ethyl acetate (5:1) to benzene:ethyl acetate (10:1) to give 1.34 g of methyl (1S)-1-acetoxymethyl-5-benzyloxy-3-t-butoxycarbonyl-1,2,3,6-tetrahydropyrrolo[3,2-e]indole-7-carboxylate. Yield, 23%. Mp. 128.5-129.5° C. (isopropyl ether). Elemental analysis: Calculated as C27H30N2O7 : C,65.57; H,6.11; N,5.66 Found: C,65.40; H,6.05; N,5.64 NMR (CDCl3) δ: 1.58 (9H, s), 2.10 (3H, s), 3.80-3.92 (2H, m), 3.92 (3H, s), 4.06 (1H, t, J=10.3 Hz), 4.15 (1H, dd, J=9.3, 11.2 Hz), 4.48 (1H, dd, J=5.4, 10.8 Hz), 5.22 (2H, s), 7.13 (1H, d, J=2.4 Hz), 7.39-7.48 (5H, m), 7.82 (1H, brs), 9.00 (1H, s). [α]D25 =-11.1° (c 0.21, methanol).

Workup

  1. concentrationThe reaction mixture was concentrated
  2. additionethyl acetate was added to the obtained residue, insoluble matter
  3. customwas removed by filtration
  4. concentrationthe obtained filtrate was concentrated
  5. customto give a residue
  6. customThe residue was then purified by silica gel column chromatography

Sources & evidence

ORD record
ord-5315fb39ff91487fb53f31a4fa4f8031
Source dataset
uspto-grants-2000_05
Patent number
US06066742

Reaction notes

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