Indole → HCID 21468966, compound

HRID 1938585Notes

Reaction equation

HRID 1938585 reaction equation
C([Li])(CC)C.Br[C:7]1[CH:8]=[C:9]2[C:13](=[CH:14][CH:15]=1)[N:12]([Si:16]([CH:23]([CH3:25])[CH3:24])([CH:20]([CH3:22])[CH3:21])[CH:17]([CH3:19])[CH3:18])[CH:11]=[CH:10]2.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(C[AlH]CC(C)C)C.Br[C:55]1[CH:62]=[CH:61][CH:60]=[CH:59][C:56]=1[C:57]#[N:58].N1C2C(=CC=CC=2)C=C1>C1COCC1.CCCCCC.[Cl-].[Na+].O.[Cl-].[Cl-].[Zn+2].C/C(/[O-])=C/C(C)=O.C/C(/[O-])=C/C(C)=O.[Ni+2].CCOCC>[C:57]([C:56]1[CH:59]=[CH:60][CH:61]=[CH:62][C:55]=1[C:7]1[CH:8]=[C:9]2[C:13](=[CH:14][CH:15]=1)[N:12]([Si:16]([CH:23]([CH3:25])[CH3:24])([CH:17]([CH3:18])[CH3:19])[CH:20]([CH3:21])[CH3:22])[CH:11]=[CH:10]2)#[N:58]

Participants

13

Reactant 6

HCID 798IndoleHCID 11776TriphenylphosphineHCID 14487Diisobutylaluminum hydrideHCID 162722-BromobenzonitrileHCID 27946525-Bromo-1-(triisopropylsilyl)-1H-indoleHCID 178418400CID 53628100

Product 1

HCID 21468966HCID 21468966, compoundYield 52.4%

Reagents, catalysts & solvents 6

HCID 3007855ZincchlorideCatalystHCID 9834912Nickel(II) acetylacetonateCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
0 °C

Procedure

sec-Butyllithium (41 mmole, 31.5 ml) was added dropwise over 10 minutes to 5-bromo-1-triisopropylsilylindole (40 mmoles, 14.0 g) in 400 ml THF at -78° C. The solution was stirred for 15 minutes. A solution of anhydrous ZnCl2 in 50 ml THF was added. The solution was warmed to 0° C. and stirred for 40 minutes. In a separate flask nickel acetylacetonate (1.5 mmole, 0.385 g) and triphenylphosphine (6.0 mmoles, 1.60 g) were dissolved in 20 ml of THF and cooled to -78° C. DIBAL mmole, 1.5 ml of 1.0M solution in hexane) was added. The solution was stirred for 10 minutes. 2-Bromobenzonitrile (39.9 mmoles, 7.26 g) was added. After stirring for minutes, the indole solution was added over a 10 minute period. The mixture was allowed to warm to room temperature, stirred for 2 hours, and then added to ether and brine. The organic phase was dried over magnesium sulfate and concentrated in vacuo. The product was chromatographed over silica gel eluted with 0-15% ether in hexane to yield 7.83 g of 5-(2-cyanophenyl)-1-triisopropylsilylindole. (MS)

Workup

  1. stirringstirred for 40 minutes
  2. temperaturecooled to -78° C
  3. stirringThe solution was stirred for 10 minutes
  4. stirringAfter stirring for minutes
  5. temperatureto warm to room temperature
  6. stirringstirred for 2 hours
  7. dry with materialThe organic phase was dried over magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. customThe product was chromatographed over silica gel
  10. washeluted with 0-15% ether in hexane

Sources & evidence

ORD record
ord-cc14e8a1e03c46db826f2517527863e5
Source dataset
uspto-grants-1997_12
Patent number
US05693633

Reaction notes

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