반응 #12012

반응 방정식

water

(4R,9aR)-6-bromo-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester

intermediate b

(4R,9aR)-6-bromo-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester

triethylborane

potassium carbonate

triethylborane

→

product

수율 89.5%

(4R,9aR)-6-Ethyl-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester

수율 89.5%

용매

N,N-dimethylformamide

THF

반응 조건

후처리

1. 1
   추출extracted twice with ethyl acetate
2. 2
   세척The combined organic phases were washed with brine
3. 3
   건조dried over magnesium sulfate
4. 4
   여과filtered
5. 5
   기타evaporated
6. 6
   기타The crude product was purified by column chromatography on silica gel (Q0.032–0.063 mm) with tert-butyl methyl ether:n-hexane (1:4) as eluant

실험 절차

To a solution of 0.70 g (1.90 mmol) (4R,9aR)-6-bromo-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester (Example 5, intermediate b) in 14 ml N,N-dimethylformamide was added 73.0 mg [1,1′-bis(diphenyphosphino)ferrocene]-dichloropalladium(II) and after 15 min, 4.8 ml of a 1M triethylborane solution in THF and 0.79 g (5.70 mmol) potassium carbonate were added. After 4 h another 2.4 ml triethylborane solution was added and the reaction mixture stirred overnight at 65 deg C. The mixture was cooled to room temperature and the suspension was poured into water and extracted twice with ethyl acetate. The combined organic phases were washed with brine, dried over magnesium sulfate, filtered and evaporated. The crude product was purified by column chromatography on silica gel (Q0.032–0.063 mm) with tert-butyl methyl ether:n-hexane (1:4) as eluant to yield the product as a colorless oil (89.5%).

출처