Ammonium Chloride → tert-Butyl 5-ethenyl-1H-indole-1-carboxylate

HRID 2249907Notes

Reaction equation

HRID 2249907 reaction equation
[Li][CH2:2]CCC.[C:6]([O:10][C:11]([N:13]1[C:21]2[C:16](=[CH:17][C:18]([CH:22]=O)=[CH:19][CH:20]=2)[CH:15]=[CH:14]1)=[O:12])([CH3:9])([CH3:8])[CH3:7].[Cl-].[NH4+]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[C:6]([O:10][C:11]([N:13]1[C:21]2[C:16](=[CH:17][C:18]([CH:22]=[CH2:2])=[CH:19][CH:20]=2)[CH:15]=[CH:14]1)=[O:12])([CH3:9])([CH3:8])[CH3:7]

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 11172622tert-Butyl 5-formyl-1H-indole-1-carboxylateHCID 178418339Butyllithium

Product 1

HCID 66890900tert-Butyl 5-ethenyl-1H-indole-1-carboxylateYield 130.5%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

T a suspension of methyltriphenylphosphonium bromide (8.1 g, 22.7 mmol) in THF (140 mL) at 0° C. was added nBuLi (1.6 M in hexanes, 14.2 mL, 22.7 mmol) dropwise over 10 min. After 10 min of stirring, a solution of the 5-formyl-indole-1-carboxylic acid tert-butyl ester (4.63 g, 14.8 mmol) in THF (20 mL) was introduced slowly over 20 min. The reaction was warmed slowly to room temperature, stirred 30 min. The reaction mixture was poured into saturated ammonium chloride and the separated aqueous phase was extracted with ethylacetate (3×100 mL). The combined organic phase was dried over sodium sulfate, filtered and concentrated. The residue was purified by chromatography (methylene chloride to 1% acetone-methylene chloride) to give 5-vinyl-indole-1-carboxylic acid tert-butyl ester (4.7 g, 100%) or similarly 6-vinyl-indole-1-carboxylic acid tert-butyl ester.

Workup

  1. stirringstirred 30 min
  2. extractionthe separated aqueous phase was extracted with ethylacetate (3×100 mL)
  3. dry with materialThe combined organic phase was dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was purified by chromatography (methylene chloride to 1% acetone-methylene chloride)

Sources & evidence

ORD record
ord-7cb2bfb3ec664fc585e0823b458889fb
Source dataset
uspto-grants-2008_01
Patent number
US07314936B2

Reaction notes

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