반응 #12042

반응 방정식

ammonium chloride

tert-butyllithium

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

acetaldehyde

→

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

용매

diethyl ether

반응 조건

후처리

1. 1
   온도After warming to −75 deg C
2. 2
   추출extracted three times with ethyl acetate
3. 3
   세척The combined organic layers were washed with brine
4. 4
   건조dried over magnesium sulfate
5. 5
   여과filtered
6. 6
   기타evaporated
7. 7
   기타The residue was chromatographed on silica gel (0.032–0.063 mm) with ethyl acetate:n-hexane (2:3) as eluant
8. 8
   기타to afford a first batch of compound
9. 9
   workup.ADDITIONThe remaining product-containing fractions
10. 10
    기타chromatographed again
11. 11
    기타to yield a second batch of compound (56.9% total)

실험 절차

A solution of 6.0 g (16.3 mmol) (4R,9aR)-6-bromo-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester in 250 ml diethyl ether was cooled to −100 deg C. and treated with 11.9 ml (17.9 mmol) tert-butyllithium (1.5 M in n-pentane). After 15 min, 1.0 ml (0.79 g, 17.9 mmol) acetaldehyde was added and the reaction was stirred for 40 min at the same temperature. After warming to −75 deg C. the reaction mixture was poured onto 10% aqueous ammonium chloride solution and extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (0.032–0.063 mm) with ethyl acetate:n-hexane (2:3) as eluant to afford a first batch of compound. The remaining product-containing fractions were pooled and chromatographed again to yield a second batch of compound (56.9% total).

출처