Carbon tetrabromide → HCID 67237765, compound

HRID 1985723Notes

Reaction equation

HRID 1985723 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:20][C@@H:19]([CH3:21])[N:18]2[C@H:10]([CH2:11][C:12]3[C:17]2=[N:16][C:15]([CH:22](O)[CH2:23][O:24][Si:25]([C:28]([CH3:31])([CH3:30])[CH3:29])([CH3:27])[CH3:26])=[CH:14][CH:13]=3)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].BrC(Br)(Br)Br.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCl>[C:1]([O:5][C:6]([N:8]1[CH2:20][C@@H:19]([CH3:21])[N:18]2[C@H:10]([CH2:11][C:12]3[C:17]2=[N:16][C:15]([CH2:22][CH2:23][O:24][Si:25]([C:28]([CH3:29])([CH3:31])[CH3:30])([CH3:27])[CH3:26])=[CH:14][CH:13]=3)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 67237961HCID 67237961, compound

Product 1

HCID 67237765HCID 67237765, compoundYield 48.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 0.70 g (4R,9aR)-6-[2-(tert-butyl-dimethyl-silanyloxy)-1-hydroxy-ethyl]-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester in 10 ml dichloromethane was added at room temperature 0.794 g tetrabromo methane and 0.628 g triphenylphosphine and the mixture was stirred at this temperature for 30 min. The reaction mixture was purified by chromatography on silica gel with heptane:ethyl acetate=2:1. The product (0.66 g) was taken up in 10 ml tetrahydrofuran. To the resulting solution was added a solution of 0.218 g potassium fluoride in 2 ml water, 0.028 g palladium acetate and 0.50 ml polymethylhydroxysilane and the mixture was stirred at room temperature for 3 h. The reaction mixture was partitioned between water and ethyl acetate, the phases were separated, the organic phase was washed with water and brine dried over sodium sulfate and evaporated. The residue was purified by chromatography on silica gel with heptane:ethyl acetate=2:1 to yield 0.329 g (4R,9aR)-6-[2-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester as slightly yellow oil (MS: 448.5 (M+H+))

Workup

  1. customThe reaction mixture was purified by chromatography on silica gel with heptane
  2. additionTo the resulting solution was added a solution of 0.218 g potassium fluoride in 2 ml water, 0.028 g palladium acetate and 0.50 ml polymethylhydroxysilane
  3. stirringthe mixture was stirred at room temperature for 3 h
  4. customThe reaction mixture was partitioned between water and ethyl acetate
  5. customthe phases were separated
  6. washthe organic phase was washed with water and brine
  7. dry with materialdried over sodium sulfate
  8. customevaporated
  9. customThe residue was purified by chromatography on silica gel with heptane

Sources & evidence

ORD record
ord-45a9f261786449dda9b6ede8e3188738
Source dataset
uspto-grants-2009_06
Patent number
US07547699B2

Reaction notes

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