تفاعل #12029

معادلة التفاعل

sodium carbonate

(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

(S)-(−)-2,2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl

benzylalcohol

sodium hydride

→

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

المذيبات

toluene

ظروف التفاعل

المعالجة

1. 1
   استخلاصextracted three times with ethyl acetate
2. 2
   غسيلThe combined organic phases were washed with brine
3. 3
   تجفيفdried over magnesium sulfate
4. 4
   ترشيحfiltered
5. 5
   أخرىAfter evaporation of the volatile components
6. 6
   أخرىthe residue was chromatographed on silica gel (0.032–0.063 mm) with ethyl acetate:n-hexane (1:4) as eluant

الإجراء التجريبي

To a solution of 3.0 g (8.15 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 30 ml toluene was added 0.20 g (0.29 mmol) (S)-(−)-2,2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl and 0.12 g (0.12 mmol) di-palladium-tris(dibenzylideneacetone)chloroform complex. After 30 min, 1.0 ml (1.06 g, 9.80 mmol) benzylalcohol and 0.70 g (16.0 mmol) sodium hydride (55–65% dispersion in oil) were added and the reaction mixture was stirred for 3.5 h at 70 deg C. After cooling to room temperature, the reaction mixture was poured onto 10% aqueous sodium carbonate solution and extracted three times with ethyl acetate. The combined organic phases were washed with brine, dried over magnesium sulfate and filtered. After evaporation of the volatile components, the residue was chromatographed on silica gel (0.032–0.063 mm) with ethyl acetate:n-hexane (1:4) as eluant.

المصدر