Sodium Carbonate → (4R,9aR)-4,6,7-Trimethyl-3,4,9,9a-tetrahydro-1 H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester

HRID 1272127

Reaction equation

HRID 1272127 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]([CH3:22])=[C:14](Br)[CH:13]=3)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[C:24](=O)([O-])[O-].[Na+].[Na+].CB1OB(C)OB(C)O1.[OH-].[Na+]>C(COC)OC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[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]([CH3:22])=[C:14]([CH3:24])[CH:13]=3)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 574072TrimethylboroxineHCID 69357585(4R,9aR)-7-Bromo-4,6-dimethyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester

Product 1

HCID 69357909(4R,9aR)-4,6,7-Trimethyl-3,4,9,9a-tetrahydro-1 H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl esterYield 66%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of 0.30 g (0.78 mmol) (4R,9aR)-7-bromo-4,6-dimethyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester (example 6, intermediate) in 15 mL dimethoxyethane was added 9 mg tetrakis(triphenylphosphine)palladium. After 20 min. 0.25 g (2.35 mmol) sodium carbonate in 8 mL water and 132 μl (0.94 mmol) trimethylboroxine were added and the reaction was stirred at 100° C. for 3 h. The reaction was cooled to room temperature then poured into 1M aqueous sodium hydroxide solution and extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate, filtered and evaporated. The residue was purified by column chromatography on silica gel with ethyl acetate:n-hexane (1:2) as eluant to give the product as a light yellow oil (66.0%).

Workup

  1. temperatureThe reaction was cooled to room temperature
  2. extractionextracted twice with ethyl acetate
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. customevaporated
  7. customThe residue was purified by column chromatography on silica gel with ethyl acetate:n-hexane (1:2) as eluant

Sources & evidence

ORD record
ord-a3d843c290264c8b80d9c6c2fa7ecab9
Source dataset
uspto-grants-2007_04
Patent number
US07208494B2

Linked notes

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