Ammonium Chloride → (3S,5R)-5-Methyl-3-((4R,5S)-4-methyl-2-oxo-5-phenyl-oxazolidine-3-carbonyl)-octanoic acid tert-butyl ester

HRID 28429노트

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HRID 28429 반응식
[CH3:1][C@@H:2]1[C@H:6]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)[O:5][C:4](=[O:13])[N:3]1[C:14](=[O:22])[CH2:15][CH2:16][C@H:17]([CH3:21])[CH2:18][CH2:19][CH3:20].C[Si]([N-][Si](C)(C)C)(C)C.[Na+].[C:33]([O:37][C:38](=[O:41])[CH2:39]Br)([CH3:36])([CH3:35])[CH3:34].[Cl-].[NH4+]>C1COCC1>[C:33]([O:37][C:38](=[O:41])[CH2:39][C@@H:15]([C:14]([N:3]1[C@H:2]([CH3:1])[C@H:6]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)[O:5][C:4]1=[O:13])=[O:22])[CH2:16][C@H:17]([CH3:21])[CH2:18][CH2:19][CH3:20])([CH3:36])([CH3:35])[CH3:34]

참가 물질

6

반응물 4

HCID 25517Ammonium ChlorideHCID 79177tert-Butyl bromoacetateHCID 2724254Sodium bis(trimethylsilyl)amideHCID 57160957(4R,5S)-4-Methyl-3-((R)-4-methyl-heptanoyl)-5-phenyl-oxazolidin-2-one

생성물 1

HCID 57207445(3S,5R)-5-Methyl-3-((4R,5S)-4-methyl-2-oxo-5-phenyl-oxazolidine-3-carbonyl)-octanoic acid tert-butyl ester수율 71.8%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

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온도
-50 °C

실험 절차

To (4R,5S)-4-methyl-3-((R)-4-methyl-heptanoyl)-5-phenyl-oxazolidin-2-one (12.1 g, 0.04 mol) in THF (200 ml) at −50° C. was added sodium bis(trimethylsilyl)amide (48 mL of a 1 M solution in THF). After 30 min t-butylbromoaceate (15.6 g, 0.08 mol) was added. The solution was stirred for 4 hours at −50° C. and then warmed to room temperature. After 16 hours a saturated aqueous solution of ammonium chloride was added and the two layers separated. The aqueous phase was extracted with ether and the combined organic phases dried (MgSO4) and concentrated. Flash chromatography (9:1 hexane/EtOAc) gave (3S,5R)-5-methyl-3-((4R,5S)-4-methyl-2-oxo-5-phenyl-oxazolidine-3-carbonyl)-octanoic acid tert-butyl ester as a white solid 12 g; 72%. [a]D=+30.2 (c 1 in CHCl3). 13C NMR (100 MHz; CDCl3) 176.47, 171.24, 152.72, 133.63, 128.87, 125.86, 80.85, 78.88, 55.34, 39.98, 38.77, 38.15, 37.58, 30.60, 28.23, 20.38, 20.13, 14.50, 14.28.

후처리

  1. temperaturewarmed to room temperature
  2. customthe two layers separated
  3. extractionThe aqueous phase was extracted with ether
  4. dry with materialthe combined organic phases dried (MgSO4)
  5. concentrationconcentrated

출처 및 근거

ORD 기록
ord-775d6eb6009242fc9d2ebddbd03eb751
출처 데이터셋
uspto-grants-2008_09
특허 번호
US07419981B2

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