Ammonium Chloride → Racemic (2R,5S,6S)-5-Azido-6-hydroxy-2-methyl-azepane-1-carboxylic acid benzyl ester

HRID 1790611ノート

反応式

HRID 1790611 の反応式
[N-:1]=[N+:2]=[N-:3].[Na+].[CH2:5]([O:12][C:13]([N:15]1[CH:22]([CH3:23])[CH2:21][CH2:20][CH:19]2[CH:17]([O:18]2)[CH2:16]1)=[O:14])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[Cl-].[NH4+]>CO.O>[CH2:5]([O:12][C:13]([N:15]1[CH2:16][CH:17]([OH:18])[CH:19]([N:1]=[N+:2]=[N-:3])[CH2:20][CH2:21][CH:22]1[CH3:23])=[O:14])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

参加物

6

反応物 3

HCID 25517Ammonium ChlorideHCID 33557Sodium AzideHCID 21036429racemic (1S,4R,7R)-4-methyl-8-oxa-3-aza-bicyclo[5.1.0]octane-3-carboxylic acid benzyl ester

生成物 1

HCID 21036431Racemic (2R,5S,6S)-5-Azido-6-hydroxy-2-methyl-azepane-1-carboxylic acid benzyl ester収率 80.1%

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 962Water溶媒

実験手順

Sodium azide (0.56 g, 8.62 mmol) was added to a solution of racemic (1S,4R,7R)-4-methyl-8-oxa-3-aza-bicyclo[5.1.0]octane-3-carboxylic acid benzyl ester (0.75 g, 2.87 mmol) and ammonium chloride (0.46 g, 8.62 mmol) in MeOH (5 ml) and H2O (0.5 ml), then was refluxed for 6 h. The reaction mixture was concentrated in vacuo by rotary evaporation, then was diluted with water (5 ml) and extracted with EtOAc (10 ml). The organic layer was then extracted with water, brine, dried with MgSO4, filtered, concentrated in vacuo by rotary evaporation, and chromatographed (silica gel, 20% EtOAc/hexanes) to yield the title compound (0.7 g, 80%): 7.39–7.30 (m, 5H), 5.15 (2H, s), 4.10–3.67 (m, 2H), 3.10 (1H, d), 1.85–1.53 (m, 4H), 1.09 (3H, d); Liquid Chromatgraphy/Electrospray mass spec: M+H+=305.2.

後処理

  1. temperaturewas refluxed for 6 h
  2. concentrationThe reaction mixture was concentrated in vacuo by rotary evaporation
  3. additionwas diluted with water (5 ml)
  4. extractionextracted with EtOAc (10 ml)
  5. extractionThe organic layer was then extracted with water, brine
  6. dry with materialdried with MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo by rotary evaporation
  9. customchromatographed (silica gel, 20% EtOAc/hexanes)

出典と根拠

ORDレコード
ord-ddaf0bbb2bfd4fa883ae90f4cfbeb0f3
出典データセット
uspto-grants-2006_07
特許番号
US07071184B2

反応ノート

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