Iodine → Acetic acid (2R,3R,4R,5R)-3,4-diacetoxy-5-(6-chloro-2-iodo-purin-9-YL)-tetrahydro-furan-2-ylmethyl ester

HRID 430393

反応式

HRID 430393 の反応式
N(OCCC(C)C)=O.[C:9]([O:12][CH2:13][C@@H:14]1[C@@H:18]([O:19][C:20](=[O:22])[CH3:21])[C@@H:17]([O:23][C:24](=[O:26])[CH3:25])[C@H:16]([N:27]2[CH:35]=[N:34][C:33]3[C:28]2=[N:29][C:30](N)=[N:31][C:32]=3[Cl:36])[O:15]1)(=[O:11])[CH3:10].II.C(I)[I:41].[O-]S([O-])(=S)=O.[Na+].[Na+]>C1COCC1.[Cu]I>[C:9]([O:12][CH2:13][C@@H:14]1[C@@H:18]([O:19][C:20](=[O:22])[CH3:21])[C@@H:17]([O:23][C:24](=[O:26])[CH3:25])[C@H:16]([N:27]2[CH:35]=[N:34][C:33]3[C:28]2=[N:29][C:30]([I:41])=[N:31][C:32]=3[Cl:36])[O:15]1)(=[O:11])[CH3:10]

参加物

8

反応物 5

HCID 807IodineHCID 6346DiiodomethaneHCID 8053Isoamyl NitriteHCID 24477Sodium ThiosulfateHCID 10788628(2R,3R,4R,5R)-2-(Acetoxymethyl)-5-(2-amino-6-chloro-9H-purin-9-yl)tetrahydrofuran-3,4-diyl diacetate

生成物 1

HCID 482588Acetic acid (2R,3R,4R,5R)-3,4-diacetoxy-5-(6-chloro-2-iodo-purin-9-YL)-tetrahydro-furan-2-ylmethyl ester

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 8028Tetrahydrofuran溶媒

実験手順

Isoamyl nitrite (5 mL, 37 mmol) was added to a mixture of 5.12 g (12 mmol) [(2R,3R,4R,5R)-3-4-diacetyloxy-5-(2-amino-6-chloropurin-9-yl)oxolan-2-yl]methyl acetate (6.3), I2 (3.04 g, 12 mmol), CH2I2 (10 mL, 124 mmol), and CuI (2.4 g, 12.6 mmol) in THF (60 mL). The mixture was heated under reflux for 45 minutes and then allowed to cool to room temperature. To this solution was added 100 ml of sat. Na2S2O3 which removed the reddish color due to iodine. The aqueous was extracted 3× with chloroform, which was pooled, dried over MgSO4, and concentrated under reduced pressure. The product was then purified over a silica gel column using CHCl3-MeOH (98:2) to collect [(2R,3R,4R,5R)-3,4-diacetyloxy-5-(6-chloro-2-iodopurin-9-yl)oxolan-2-yl]methyl acetate (6.4) (80% crystallized from EtOH). 1H NMR (300 MHz, CDCl3) δ8.20 (s, 1H H-8), 6.17 (d, J=5.41 Hz, 1H, H-1′), 5.75 (t, J=5.39 Hz, 1H, H-2′), 5.56 (t, J=5.40 Hz, 1H, H-3′), 4.38 (m, 3H, H-4′,5′), 2.14 (s, 1H, Ac), 2.11 (s, 1H, Ac), 2.10 (s, 1H, Ac).

後処理

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 45 minutes
  3. customremoved the reddish color due to iodine
  4. extractionThe aqueous was extracted 3× with chloroform, which
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated under reduced pressure
  7. customThe product was then purified over a silica gel column
  8. customto collect [(2R,3R,4R,5R)-3,4-diacetyloxy-5-(6-chloro-2-iodopurin-9-yl)oxolan-2-yl]methyl acetate (6.4) (80% crystallized from EtOH)

出典と根拠

ORDレコード
ord-15c117cb2d8141b2855e4896848ea6b4
出典データセット
uspto-grants-2001_11
特許番号
US06322771B1

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