(Methoxymethyl)phosphonium chloride → (2S,4S,5S)-4-methoxy-5-methyl-3-methoxymethylene-2-nonyltetrahydro-2H-pyran

HRID 2399565ノート

反応式

HRID 2399565 の反応式
[Cl-].[CH3:2][O:3][CH2:4][PH3+].[Li]CCCC.[CH3:11][O:12][C@H:13]1[C@@H:18]([CH3:19])[CH2:17][O:16][C@@H:15]([CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])[C:14]1=O>O1CCCC1.C(OCC)(=O)C>[CH3:2][O:3][C@H:4]1[C@@H:18]([CH3:19])[CH2:17][O:16][C@@H:15]([CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])[C:14]1=[CH:13][O:12][CH3:11]

参加物

6

反応物 3

HCID 22258747(Methoxymethyl)phosphonium chlorideHCID 57073235(2S,4S,5S)-4-methoxy-5-methyl-2-nonyltetrahydro-2H-pyran-3-oneHCID 178418339Butyllithium

生成物 1

HCID 57150748(2S,4S,5S)-4-methoxy-5-methyl-3-methoxymethylene-2-nonyltetrahydro-2H-pyran収率 83%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
0 °C

実験手順

To a stirred suspension of methoxymethylphosphonium chloride (1,130 mg) in dry tetrahydrofuran (3 ml) there was added n-BuLi (1.9 ml, 1.6M in n-hexane) at 0° C. After the mixture was stirred at 0° C. for 30 min, a solution of (2S,4S,5S)-4-methoxy-5-methyl-2-nonyltetrahydro-2H-pyran-3-one (273 mg) in dry tetrahydrofuran (3 ml) was added to the resulting deep orange solution. After 30 min, the mixture was allowed to warm to room temperature, and stirred for an additional 2 hrs. The reaction was quenched by addition of saturated aqueous ammonium chloride solution. The mixture was extracted with diethyl ether, and the combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated. Purification of the residue by silica gel chromatography (n-hexane: ethyl acetate=10:1 as an eluent) gave (2S,4S,5S)-4-methoxy-5-methyl-3-methoxymethylene-2-nonyltetrahydro-2H-pyran (249 mg,83% yield).

後処理

  1. waitAfter 30 min
  2. temperatureto warm to room temperature
  3. stirringstirred for an additional 2 hrs
  4. customThe reaction was quenched by addition of saturated aqueous ammonium chloride solution
  5. extractionThe mixture was extracted with diethyl ether
  6. washthe combined organic extracts were washed with brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customPurification of the residue by silica gel chromatography (n-hexane

出典と根拠

ORDレコード
ord-ade2f49cb44a4d4b8d358c01030ef2d0
出典データセット
uspto-grants-1995_09
特許番号
US05449785

反応ノート

読み込み中…