Potassium Cyanide → 2'-Oxo-1'-pentyl-1',2'-dihydrospiro[furo[2,3-f][1,3]benzodioxole-7,3'-indole]-4'-carbonitrile

HRID 425724Notes

Reaction equation

HRID 425724 reaction equation
Br[C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[C:4]1([C:20]3=[CH:21][C:22]4[O:26][CH2:25][O:24][C:23]=4[CH:27]=[C:19]3[O:18][CH2:17]1)[C:5](=[O:16])[N:6]2[CH2:11][CH2:12][CH2:13][CH2:14][CH3:15].C(P(C(C)(C)C)C1C=CC=CC=1C1C=CC=CC=1)(C)(C)C.C([Sn]([C:62]#[N:63])(CCCC)CCCC)CCC.[C-]#N.[K+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[O:16]=[C:5]1[C:4]2([C:20]3=[CH:21][C:22]4[O:26][CH2:25][O:24][C:23]=4[CH:27]=[C:19]3[O:18][CH2:17]2)[C:3]2[C:2]([C:62]#[N:63])=[CH:10][CH:9]=[CH:8][C:7]=2[N:6]1[CH2:11][CH2:12][CH2:13][CH2:14][CH3:15]

Participants

6

Reactant 4

HCID 9032Potassium CyanideHCID 200512Stannanecarbonitrile, tributyl-HCID 27342152-(Di-tert-butylphosphino)biphenylHCID 592633394'-bromo-1'-pentylspiro[furo[2,3-f][1,3]benzodioxole-7,3'-indol]-2'(1'H)one

Product 1

HCID 592634652'-Oxo-1'-pentyl-1',2'-dihydrospiro[furo[2,3-f][1,3]benzodioxole-7,3'-indole]-4'-carbonitrileYield 34.7%

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Procedure

A mixture of 4′-bromo-1′-pentylspiro[furo[2,3-f][1,3]benzodioxole-7,3′-indol]-2′(1′H)-one (0.10 g, 0.23 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.21 g, 0.23 mmol) and 2-(di-tert-butylphosphino)biphenyl (0.07, 0.23 mmol), tributyltin cyanide (0.07 g, 0.23 mmol) and potassium cyanide (0.02 g, 0.23 mmol) was purged with nitrogen and anhydrous acetonitrile (10.0 mL) was added. The reaction mixture was refluxed for 16 h. After cooling down to ambient temperature, the reaction mixture was diluted with ethyl acetate (20.0 mL), washed with water (20.0 mL), brine (20.0 mL), dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo to dryness. The brown residue was subjected to column chromatography eluting with ethyl acetate/hexane (65%) to give the title compound (0.03 g, 33%) which was recrystallized from ether to get a colorless solid: mp 128-129° C.; 1H NMR (300 MHz, CDCl3) δ 9.10 (s, 1H), 7.42-7.37 (m, 1H), 7.29-7.27 (m, 1H), 7.09 (d, 1H), 6.53 (s, 1H), 6.03 (s, 1H), 5.87 (dd, 2H), 4.91 (q, 2H), 3.86-3.63 (m, 2H), 1.74-1.62 (m, 2H), 1.43-1.26 (m, 4H), 0.89 (t, 3H); 13C NMR (75 MHz, CDCl3) δ 176.5, 157.1, 149.5, 143.5, 142.4, 135.4, 129.7, 128.3, 126.4, 116.3, 114.8, 112.3, 108.8, 102.2, 93.7, 78.7, 58.3, 40.6, 28.9, 26.7, 22.2, 13.9; MS (ES+) m/z 377.5 (M+1).

Workup

  1. customwas purged with nitrogen and anhydrous acetonitrile (10.0 mL)
  2. additionwas added
  3. temperatureThe reaction mixture was refluxed for 16 h
  4. additionthe reaction mixture was diluted with ethyl acetate (20.0 mL)
  5. washwashed with water (20.0 mL), brine (20.0 mL)
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationThe filtrate was concentrated in vacuo to dryness
  9. washeluting with ethyl acetate/hexane (65%)

Sources & evidence

ORD record
ord-6df8c50026bf4777a4b8189a17237c8f
Source dataset
uspto-grants-2012_01
Patent number
US08106087B2

Reaction notes

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