Hydrochloric Acid → 2,6-Anhydro-3,4,5-trideoxy-3-[[(1,1-dimethylethoxy)carbonyl]amino]-D-erythro-hexonic acid

HRID 497486

반응식

HRID 497486 반응식
[C:1]([O:5][C:6](=[O:16])[NH:7][C@@H:8]1[CH2:13][CH2:12][CH2:11][O:10][C@H:9]1[CH:14]=[O:15])([CH3:4])([CH3:3])[CH3:2].[Br-].[K+].Cl[O-].[Na+].C(=O)(O)[O-:23].[Na+].[OH-].[Na+].Cl>C(Cl)Cl.[Br-].C[N+](C)(C)C.O>[C:1]([O:5][C:6]([NH:7][C@@H:8]1[CH2:13][CH2:12][CH2:11][O:10][C@H:9]1[C:14]([OH:23])=[O:15])=[O:16])([CH3:4])([CH3:2])[CH3:3]

참가 물질

10

반응물 6

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 253877Potassium BromideHCID 516892Sodium BicarbonateHCID 23665760Sodium HypochloriteHCID 59094967[(2R,3R)-2-formyl-tetrahydro-pyran-3-yl]-carbamic acid tert-butyl ester

생성물 1

HCID 590950282,6-Anhydro-3,4,5-trideoxy-3-[[(1,1-dimethylethoxy)carbonyl]amino]-D-erythro-hexonic acid수율 89.5%

시약·촉매·용매 3

HCID 66137Tetramethylammonium bromide촉매HCID 962Water용매HCID 6344Dichloromethane용매

반응 조건

온도
0 °C

실험 절차

To a stirring solution of [(2R,3R)-2-formyl-tetrahydro-pyran-3-yl]-carbamic acid tert-butyl ester (57.7 mg, 0.251 mmol)in methylene chloride (2 mL) was added tetramethyl-ammonium bromide (4.1 mg, 0.012 mmol) and 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical (1 mg, 0.003 mmol), followed by a solution of potassium bromide (3 mg, 0.03 mmol) in water (1 mL). Upon cooling the mixture to 0° C., aqueous sodium hypochlorite (3.6 mL, 0.35 M) made pH 8.6 with sodium bicarbonate (50 mg/mL of 0.35 M NaOCl) was added, and the resulting yellow/orange mixture was stirred vigorously for 5 min. The reaction was poured into 1N aqueous sodium hydroxide (50 mL), acidified with 1N aqueous hydrogen chloride (55 mL), and washed with ethyl acetate (3×50 mL). The combined organic layers were dried over sodium sulfate, concentrated in vacuo, and the resulting residue was purified by flash chromatography (SiO2, 30-50% ethyl acetate in hexanes then 70% ethyl acetate in hexanes containing 5% acetic acid and 1% methanol) to give the desired product (55.5 mg, 89.5%) as a foamy solid. MS (ESI), m−/z: (M−H)−=244.

후처리

  1. additionwas added
  2. washwashed with ethyl acetate (3×50 mL)
  3. dry with materialThe combined organic layers were dried over sodium sulfate
  4. concentrationconcentrated in vacuo
  5. customthe resulting residue was purified by flash chromatography (SiO2, 30-50% ethyl acetate in hexanes

출처 및 근거

ORD 기록
ord-004dc5e157ef4ce0a0f871421f16d70f
출처 데이터셋
uspto-grants-2005_09
특허 번호
US06949546B2

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