Pentane → 3-bromo-1-(tert-butyl-dimethyl-silanyl)-5-(tert-butyl-dimethyl-silanyloxy)-1H-indole

HRID 1767959Notes

Reaction equation

HRID 1767959 reaction equation
[Li]CCCC.CCCCC.[C:11]([Si:15]([CH3:27])([CH3:26])[O:16][C:17]1[CH:18]=[C:19]2[C:23](=[CH:24][CH:25]=1)[NH:22][CH:21]=[CH:20]2)([CH3:14])([CH3:13])[CH3:12].[Si:28](Cl)([C:31]([CH3:34])([CH3:33])[CH3:32])([CH3:30])[CH3:29].[Br:36]N1C(=O)CCC1=O>C1COCC1.C(OCC)C>[Br:36][C:20]1[C:19]2[C:23](=[CH:24][CH:25]=[C:17]([O:16][Si:15]([C:11]([CH3:14])([CH3:13])[CH3:12])([CH3:27])[CH3:26])[CH:18]=2)[N:22]([Si:28]([C:31]([CH3:34])([CH3:33])[CH3:32])([CH3:30])[CH3:29])[CH:21]=1

Participants

8

Reactant 5

HCID 8003PentaneHCID 28928tert-Butyldimethylsilyl chlorideHCID 67184N-bromobutanimideHCID 222508175-(tert-Butyldimethylsilyloxy)-1H-indoleHCID 178418339Butyllithium

Product 1

HCID 236144893-bromo-1-(tert-butyl-dimethyl-silanyl)-5-(tert-butyl-dimethyl-silanyloxy)-1H-indoleYield 77.2%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A 1.6 M solution of BuLi in pentane (30.7 ml, 49.2 mmol) was added to a solution of 5-(tert-butyl-dimethyl-silanyloxy)-1H-indole (9.36 g, 37.8 mmol) in THF (190 ml) at −78° C. within 20 min under an argon atmosphere. The reaction mixture was stirred for 20 min at −78° C. tert-Butyldimethylsilyl chloride (7.64 g, 49.2 mmol) was added and the reaction mixture was stirred for 10 min at −78° C. and for 1 h at RT. The mixture was chilled to −78° C., N-bromosuccinimide (7.64 g, 41.6 mmol) was added and the solution was stirred for 1 h at −78° C. and for 1 h at RT. Diethyl ether was added and the mixture was washed with saturated aqueous NaHCO3 solution and water. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The crude product was purified by column chromatography (silica gel, CH2Cl2/heptane 1:19) to give 12.87 g (29.2 mmol, 77%) 3-bromo-1-(tert-butyl-dimethyl-silanyl)-5-(tert-butyl-dimethyl-silanyloxy)-1H-indole.

Workup

  1. additionwas added
  2. temperatureThe mixture was chilled to −78° C.
  3. stirringthe solution was stirred for 1 h at −78° C. and for 1 h at RT
  4. washthe mixture was washed with saturated aqueous NaHCO3 solution and water
  5. dry with materialThe organic layer was dried over sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe crude product was purified by column chromatography (silica gel, CH2Cl2/heptane 1:19)

Sources & evidence

ORD record
ord-86a94204547344e99d9335195e1d63b9
Source dataset
uspto-grants-2007_06
Patent number
US07235572B2

Reaction notes

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