Pentane → 3-bromo-1-(tert-butyl-dimethyl-silanyl)-6-(tert-butyl-dimethyl-silanyloxy)-1H-indole

HRID 1767934Notes

Reaction equation

HRID 1767934 reaction equation
[Li]CCCC.CCCCC.[C:11]([Si:15]([CH3:27])([CH3:26])[O:16][C:17]1[CH:25]=[C:24]2[C:20]([CH:21]=[CH:22][NH:23]2)=[CH:19][CH:18]=1)([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:21]1[C:20]2[C:24](=[CH:25][C:17]([O:16][Si:15]([C:11]([CH3:14])([CH3:13])[CH3:12])([CH3:27])[CH3:26])=[CH:18][CH:19]=2)[N:23]([Si:28]([C:31]([CH3:34])([CH3:33])[CH3:32])([CH3:30])[CH3:29])[CH:22]=1

Participants

8

Reactant 5

HCID 8003PentaneHCID 28928tert-Butyldimethylsilyl chlorideHCID 67184N-bromobutanimideHCID 222508166-((tert-butyldimethylsilyl)oxy)-1H-indoleHCID 178418339Butyllithium

Product 1

HCID 236144903-bromo-1-(tert-butyl-dimethyl-silanyl)-6-(tert-butyl-dimethyl-silanyloxy)-1H-indoleYield 74.1%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A 1.6 M solution of BuLi in pentane (6.57 ml, 10.5 mmol) was added to a solution of 6-(tert-butyl-dimethyl-silanyloxy)-1H-indole (2 g, 8.1 mmol) in THF (40 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 (1.6 g, 10.5 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 (1.6 g, 8.9 mmol) was added and stirring was continued for 1 h at −78° C. and for 1 h at RT. The solution was diluted with diethyl ether and washed with saturated aqueous NaHCO3 solution and water. The ether phase was dried over sodium sulfate, concentrated under reduced pressure and the residue was purified by column chromatography (silica gel, n-heptane/ethyl acetate 1:19) to give 2.64 g (6 mmol, 74%) 3-bromo-1-(tert-butyl-dimethyl-silanyl)-6-(tert-butyl-dimethyl-silanyloxy)-1H-indole as brown solid.

Workup

  1. additionwas added
  2. temperatureThe mixture was chilled to −78° C.
  3. stirringstirring
  4. waitwas continued for 1 h at −78° C. and for 1 h at RT
  5. washwashed with saturated aqueous NaHCO3 solution and water
  6. dry with materialThe ether phase was dried over sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customthe residue was purified by column chromatography (silica gel, n-heptane/ethyl acetate 1:19)

Sources & evidence

ORD record
ord-5b8ffa335ac7487fbc625e8eec87e620
Source dataset
uspto-grants-2007_06
Patent number
US07235572B2

Reaction notes

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