Sodium borohydride → [(1R,2R,3S,4R,5S)-3,4-dibenzyloxy-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-2-hydroxy-6,8-dioxabicyclo[3.2.1]octan-1-yl]methyl acetate

HRID 1055617ノート

反応式

HRID 1055617 の反応式
[C:1]([O:4][CH2:5][C@:6]12[O:13][C@:10]([C:14]3[CH:19]=[CH:18][C:17]([Cl:20])=[C:16]([CH2:21][C:22]4[CH:27]=[CH:26][C:25]([O:28][CH2:29][CH3:30])=[CH:24][CH:23]=4)[CH:15]=3)([O:11][CH2:12]1)[C@H:9]([O:31][CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[C@@H:8]([O:39][CH2:40][C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)[C:7]2=[O:47])(=[O:3])[CH3:2].[BH4-].[Na+]>CO.O1CCCC1>[C:1]([O:4][CH2:5][C@:6]12[O:13][C@:10]([C:14]3[CH:19]=[CH:18][C:17]([Cl:20])=[C:16]([CH2:21][C:22]4[CH:27]=[CH:26][C:25]([O:28][CH2:29][CH3:30])=[CH:24][CH:23]=4)[CH:15]=3)([O:11][CH2:12]1)[C@H:9]([O:31][CH2:32][C:33]1[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=1)[C@@H:8]([O:39][CH2:40][C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)[C@H:7]2[OH:47])(=[O:3])[CH3:2]

参加物

4

反応物 2

HCID 4311764Sodium borohydrideHCID 131736405[(1R,3R,4R,5S)-3,4-dibenzyloxy-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-2-oxo-6,8-dioxabicyclo[3.2.1]octan-1-yl]methyl acetate

生成物 1

HCID 122610451[(1R,2R,3S,4R,5S)-3,4-dibenzyloxy-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-2-hydroxy-6,8-dioxabicyclo[3.2.1]octan-1-yl]methyl acetate収率 100%

試薬・触媒・溶媒 1

HCID 21899815MeOH tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

To a solution of [(1R,3R,4R,5S)-3,4-dibenzyloxy-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-2-oxo-6,8-dioxabicyclo[3.2.1]octan-1-yl]methyl acetate 28h (4.09 g, 6.2 mmol) in an anhydrous methanol/tetrahydrofuran mixture (v/v=3/1, 20 mL) was added sodium borohydride (278 mg, 7.5 mmol) at 0° C. The mixture was stirred at 0° C. for 5 min, then quenched with water at 0° C. and adjusted with saturated aqueous ammonium chloride till pH becomes 7. The mixture was concentrated in vacuo to remove parts of the solvent. The resulting mixture was extracted with ethyl acetate (100 mL×3). The combined organic layers were washed with saturated aqueous sodium chloride (100 mL×3), dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo to give the title compound 28i as pale yellow oil (4.08 g, 100%). The compound was characterized by the following spectroscopic data: 1H NMR (400 MHz, DMSO-d6) δ (ppm): 7.50 (m, 2H), 7.38 (d, 3H), 7.30 (m, 3H), 7.21 (m, 3H), 7.03 (d, 2H), 6.80 (d, 2H), 6.74 (d, 2H), 5.17 (d, 1H), 4.75 (d, 1H), 4.52 (d, 1H), 4.41 (d, 1H), 4.34 (d, 1H), 4.27 (d, 1H), 4.13 (d, 1H), 3.99 (m, 2H), 3.94 (m, 3H), 3.85 (m, 3H), 3.71 (d, 1H), 2.01 (s, 3H), 1.28 (t, 3H).

後処理

  1. customquenched with water at 0° C.
  2. concentrationThe mixture was concentrated in vacuo
  3. customto remove parts of the solvent
  4. extractionThe resulting mixture was extracted with ethyl acetate (100 mL×3)
  5. washThe combined organic layers were washed with saturated aqueous sodium chloride (100 mL×3)
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationThe filtrate was concentrated in vacuo

出典と根拠

ORDレコード
ord-f153bfcb3f304fce92a381ae77a132d6
出典データセット
uspto-grants-2016_07
特許番号
US09394329B2

反応ノート

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