Boron trifluoride etherate → diethyl (((2S,3S,4R,5R,6S)-3,4,5-tris(benzyloxy)-6-methyltetrahydro-2H-pyran-2-yl)methyl)phosphonate

HRID 522167ノート

反応式

HRID 522167 の反応式
B(F)(F)F.CCOCC.C([SiH](CC)CC)C.[CH2:17]([O:24][C@H:25]1[C@H:30]([O:31][CH2:32][C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C@H:29]([O:39][CH2:40][C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)[C@H:28]([CH3:47])[O:27][C@@:26]1([CH2:49][P:50](=[O:57])([O:54][CH2:55][CH3:56])[O:51][CH2:52][CH3:53])O)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>C(#N)C>[CH2:17]([O:24][C@H:25]1[C@H:30]([O:31][CH2:32][C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C@H:29]([O:39][CH2:40][C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)[C@H:28]([CH3:47])[O:27][C@@H:26]1[CH2:49][P:50](=[O:57])([O:51][CH2:52][CH3:53])[O:54][CH2:55][CH3:56])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

参加物

5

反応物 3

HCID 8000Boron trifluoride etherateHCID 12052TriethylsilaneHCID 11786599diethyl (((2S,3S,4R,5R,6S)-3,4,5-tris(benzyloxy)-2-hydroxy-6-methyltetrahydro-2H-pyran-2-yl)methyl)phosphonate

生成物 1

HCID 11238435diethyl (((2S,3S,4R,5R,6S)-3,4,5-tris(benzyloxy)-6-methyltetrahydro-2H-pyran-2-yl)methyl)phosphonate収率 90.2%

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

反応条件

温度
0 °C

実験手順

Boron trifluoride diethyl etherate (0.079 mL, 0.644 mmol, commercially available from Sigma Aldrich) and triethylsilane (0.103 mL, 0.644 mmol, Sigma Aldrich) were added to a stirred solution of diethyl (((2S,3S,4R,5R,6S)-3,4,5-tris(benzyloxy)-2-hydroxy-6-methyltetrahydro-2H-pyran-2-yl)methyl)phosphonate (0.251 g, 0.429 mmol) in acetonitrile (2 mL) at 0° C. under an argon atmosphere. The reaction mixture was then stirred at 0° C. for 5 h. The reaction mixture was next partitioned between EtOAc and saturated aqueous sodium bicarbonate. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The resulting oil was purified by silica gel chromatography (30 to 100% EtOAc/hexanes gradient) to give diethyl (((2S,3S,4R,5R,6S)-3,4,5-tris(benzyloxy)-6-methyltetrahydro-2H-pyran-2-yl)methyl)phosphonate as a colorless oil (0.220 g, 90% yield). 1H NMR (400 MHz, CDCl3): δ ppm 1.14 (d, J=6.26 Hz, 3 H) 1.26 (td, J=7.04, 1.96 Hz, 6 H) 1.92 (td, J=15.75, 9.78 Hz, 1 H) 2.29 (ddd, J=19.95, 15.36, 1.47 Hz, 1 H) 3.53 (q, J=6.39 Hz, 1H) 3.56-3.70 (m, 4 H) 3.98-4.11 (m, 4 H) 4.63-4.77 (m, 4 H) 4.97 (dd, J=11.44, 1.86 Hz, 2 H) 7.26-7.39 (m, 15 H).

後処理

  1. customThe reaction mixture was next partitioned between EtOAc and saturated aqueous sodium bicarbonate
  2. customThe organic layer was separated
  3. dry with materialdried over anhydrous magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe resulting oil was purified by silica gel chromatography (30 to 100% EtOAc/hexanes gradient)

出典と根拠

ORDレコード
ord-77c1706d569f4b73867cd52f4ce6ec98
出典データセット
uspto-grants-2016_05
特許番号
US09328134B2

反応ノート

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