Diisopropylamine → 1-ethyl-6-methoxy-2-tributylstannanyl-1H-indole-3-carbonitrile

HRID 907100Notes

Reaction equation

HRID 907100 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[Li+].CC([N-]C(C)C)C.[CH2:21]([N:23]1[C:31]2[C:26](=[CH:27][CH:28]=[C:29]([O:32][CH3:33])[CH:30]=2)[C:25]([C:34]#[N:35])=[CH:24]1)[CH3:22].[CH2:36]([Sn:40](I)([CH2:45][CH2:46][CH2:47][CH3:48])[CH2:41][CH2:42][CH2:43][CH3:44])[CH2:37][CH2:38][CH3:39]>C1COCC1>[CH2:21]([N:23]1[C:31]2[C:26](=[CH:27][CH:28]=[C:29]([O:32][CH3:33])[CH:30]=2)[C:25]([C:34]#[N:35])=[C:24]1[Sn:40]([CH2:41][CH2:42][CH2:43][CH3:44])([CH2:45][CH2:46][CH2:47][CH3:48])[CH2:36][CH2:37][CH2:38][CH3:39])[CH3:22]

Participants

7

Reactant 5

HCID 7912DiisopropylamineHCID 23765Tributyltin iodideHCID 2724682Lithium diisopropylamide2×HCID 116441001-ethyl-6-methoxy-1H-indole-3-carbonitrileHCID 178418339Butyllithium

Product 1

HCID 594249491-ethyl-6-methoxy-2-tributylstannanyl-1H-indole-3-carbonitrileYield 98.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A solution of THF (60 mL) and diisopropylamine (5.5 mL, 39 mmol) was cooled to −78° C. n-Butyllithium (14.5 mL, 2.5M in hexanes, 36.2 mmol) was added dropwise over 5 minutes. The LDA mixture was stirred at −78° C. for 10 minutes, and then at 0° C. for 20 minutes. The solution was re-cooled to −78° C. 1-ethyl-6-methoxy-1H-indole-3-carbonitrile (5.0 g, 25 mmol), prepared as in example 1A, was taken up in THF (30 mL) and added dropwise to the LDA mixture over 15 minutes. The reaction was stirred at −78° C. for 10 minutes, and at 0° C. for 30 minutes. Once again, the reaction mixture was cooled to −78° C. Tributyltin iodide (10 mL, 35 mmol) was added dropwise. This was stirred at −78° C. for 15 minutes, and then at 0° C. for 30 minutes. The reaction mixture was absorbed onto silica gel and concentrated. Purification by chromatography (CH2Cl2) yielded 1-ethyl-6-methoxy-2-tributylstannanyl-1H-indole-3-carbonitrile (12.05 g, 98%).

Workup

  1. additionwas added dropwise over 5 minutes
  2. waitat 0° C. for 30 minutes
  3. temperatureOnce again, the reaction mixture was cooled to −78° C
  4. stirringThis was stirred at −78° C. for 15 minutes
  5. waitat 0° C. for 30 minutes
  6. customThe reaction mixture was absorbed onto silica gel
  7. concentrationconcentrated
  8. customPurification by chromatography (CH2Cl2)

Sources & evidence

ORD record
ord-4a2e024dce784c17b0bb95d5b1d8241c
Source dataset
uspto-grants-2011_09
Patent number
US08013006B2

Reaction notes

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