Reaktion #12029

Reaktionsgleichung

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

Lösungsmittel

toluene

Reaktionsbedingungen

Aufarbeitung

1. 1
   Extraktionextracted three times with ethyl acetate
2. 2
   WaschenThe combined organic phases were washed with brine
3. 3
   Trocknendried over magnesium sulfate
4. 4
   Filtrationfiltered
5. 5
   SonstigeAfter evaporation of the volatile components
6. 6
   Sonstigethe residue was chromatographed on silica gel (0.032–0.063 mm) with ethyl acetate:n-hexane (1:4) as eluant

Vorschrift

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.

Quelle