반응 #87479
ord-d6d5b1f3def849d68028b09b3407c755
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후처리
- 1온도the reaction mixture was heated
- 2온도at reflux under nitrogen
- 3기타The layers were separated
- 4추출the aqueous layer was extracted two additional times with dichloromethane (25 mL)
- 5세척The combined organic layers were washed with brine (20 mL)
- 6건조dried over magnesium sulfate
- 7여과filtered through a pad of celite
- 8농축concentrated under reduced pressure
- 9기타The crude material was chromatographed with the Biotage SP4 automated chromatography unit (SNAP 25 g silica gel column)
- 10세척eluting with a gradient of 0-80% ethyl acetate in heptane
실험 절차
To a solution of acetic acid (1R,2S,3S,4R,5S)-3,4-diacetoxy-1-acetoxymethyl-5-[4-chloro-3-(4-ethoxy-benzyl)-phenyl]-6,8-dioxa-bicyclo[3.2.1]oct-2-yl ester (Example 2; 344 mg, 0.569 mmol) in carbon tetrachloride (8 mL) was added N-bromosuccinimide (159 mg, 0.893 mmol) followed by the addition of 2,2′-azobisisobutyronitrile (AIBN, 8 mg, 0.05 mmol) and the reaction mixture was heated at reflux under nitrogen. After 16 hours, the reaction mixture was cooled to room temperature, water (50 mL) and dichloromethane (25 mL) were added and the resulting mixture was stirred for 24 hours at room temperature. The layers were separated and the aqueous layer was extracted two additional times with dichloromethane (25 mL). The combined organic layers were washed with brine (20 mL), dried over magnesium sulfate, filtered through a pad of celite, and concentrated under reduced pressure. The crude material was chromatographed with the Biotage SP4 automated chromatography unit (SNAP 25 g silica gel column) eluting with a gradient of 0-80% ethyl acetate in heptane to produce 316 mg (89% yield) of acetic acid (1R,2S,3S,4R,5S)-3,4-diacetoxy-1-acetoxymethyl-5-{4-chloro-3-[(4-ethoxy-phenyl)-hydroxy-methyl]-phenyl}6,8-dioxa-bicyclo[3.2.1]oct-2-yl ester as a mixture of diastereoisomers at the bis-benzylic position.