Dimethylformamide → 2'-Oxo-1',2'-dihydrospiro[furo[2,3-f][1,3]benzodioxole-7,3'-indole]-7'-carbonitrile

HRID 2385446Notes

Reaction equation

HRID 2385446 reaction equation
Br[C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:10]=1[NH:9][C:8](=[O:11])[C:7]12[C:15]2=[CH:16][C:17]3[O:21][CH2:20][O:19][C:18]=3[CH:22]=[C:14]2[O:13][CH2:12]1.[CH3:23][N:24](C)C=O>[C-]#N.[Zn+2].[C-]#N.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[O:11]=[C:8]1[C:7]2([C:15]3=[CH:16][C:17]4[O:21][CH2:20][O:19][C:18]=4[CH:22]=[C:14]3[O:13][CH2:12]2)[C:6]2[C:10](=[C:2]([C:23]#[N:24])[CH:3]=[CH:4][CH:5]=2)[NH:9]1

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 593525017'-bromospiro[furo[2,3-f][1,3]benzodioxole-7,3'-indol]-2'(1'H)-one

Product 1

HCID 593522642'-Oxo-1',2'-dihydrospiro[furo[2,3-f][1,3]benzodioxole-7,3'-indole]-7'-carbonitrileYield 76%

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Procedure

To a suspended mixture of 7′-bromospiro[furo[2,3-f][1,3]benzodioxole-7,3′-indol]-2′(1′H)-one (0.44 g, 1.2 mmol) and zinc cyanide (0.28 g, 2.4 mmol) in anhydrous N,N-dimethylformamide (12 mL) was added tetrakis(triphenylphosphine)palladium (0.14 g, 0.12 mmol). The reaction mixture was refluxed for 3 h. The solid was filtered and washed with ethyl acetate (40 mL). The filtrate was concentrated in vacuo to dryness. The residue was purified by column chromatography with ethyl acetate in hexanes (20% to 30% gradient) to afford 2′-oxo-1′,2′-dihydrospiro[furo[2,3-f][1,3]benzodioxole-7,3′-indole]-7′-carbonitrile (0.28 g, 76%) as a colorless solid: mp 205-207° C.; 1H NMR (300 MHz, DMSO-d6) δ11.55 (s, 1H), 7.62 (dd, J=8.0 Hz, 1.1 Hz, 1H), 7.41 (d, J=7.0 Hz, 1H), 7.12-7.07 (m, 1H), 6.69 (s, 1H), 6.44 (s, 1H), 5.93 (dd, J=3.4, 0.8 Hz, 2H), 4.78 (d, J=9.5 Hz, 1H), 4.67 (d, J=9.5 Hz, 1H); 13C NMR (75 MHz, DMSO-d6) δ178.4, 155.4, 148.3, 145.2, 141.7, 133.8, 131.6, 128.3, 122.5, 118.9, 115.9, 103.2, 101.3, 93.1, 92.6, 79.6, 57.5; MS (ES+) m/z 307.3 (M+1).

Workup

  1. temperatureThe reaction mixture was refluxed for 3 h
  2. filtrationThe solid was filtered
  3. washwashed with ethyl acetate (40 mL)
  4. concentrationThe filtrate was concentrated in vacuo to dryness
  5. customThe residue was purified by column chromatography with ethyl acetate in hexanes (20% to 30% gradient)

Sources & evidence

ORD record
ord-7dff741630ef46668c6a638f0c2b4086
Source dataset
uspto-grants-2012_09
Patent number
US08263606B2

Reaction notes

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