Chlorotrimethylsilane → (S)-tert-butyl 4-((R)-4-ethoxy-4-oxobutan-2-yl)-2,2-dimethyloxazolidine-3-carboxylate

HRID 970637

反応式

HRID 970637 の反応式
[Li][CH3:2].[Li+].[Br-].C[Si](Cl)(C)C.[CH2:10]([O:12][C:13](=[O:30])/[CH:14]=[CH:15]/[C@H:16]1[CH2:20][O:19][C:18]([CH3:22])([CH3:21])[N:17]1[C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])[CH3:11].[Cl-].[NH4+].[OH-].[NH4+]>C1COCC1.[Cu]I>[CH2:10]([O:12][C:13](=[O:30])[CH2:14][C@H:15]([C@H:16]1[CH2:20][O:19][C:18]([CH3:22])([CH3:21])[N:17]1[C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])[CH3:2])[CH3:11]

参加物

8

反応物 5

HCID 6397ChlorotrimethylsilaneHCID 82050Lithium BromideHCID 10732902(S,E)-tert-butyl 4-(3-ethoxy-3-oxoprop-1-enyl)-2,2-dimethyloxazolidine-3-carboxylateHCID 21863491Ammonium chloride ammonium hydroxideHCID 178418348HCID 178418348、化合物

生成物 1

HCID 11336032(S)-tert-butyl 4-((R)-4-ethoxy-4-oxobutan-2-yl)-2,2-dimethyloxazolidine-3-carboxylate

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

To CuI (3.36 g, 17.64 mmol) in THF (15 mL) was added at −78° C. MeLi.LiBr (1.5M in ether, 23.5 mL, 35.28 mmol), and the resulting mixture was stirred at −78° C. for 15 min. TMSCl (1.52 mL, 17.64 mmol) and Me2CuLi (generated above) were added in sequence at −78° C. to (S,E)-tert-butyl 4-(3-ethoxy-3-oxoprop-1-enyl)-2,2-dimethyloxazolidine-3-carboxylate (0.88 g, 2.94 mmol), and the resulting mixture was slowly warmed up to rt. Ammonium chloride-ammonium hydroxide buffer (pH ˜8) was added to the reaction mixture. The mixture was extracted with ether, washed with brine, dried over sodium sulfate, and concentrated. Flash chromatography (silica gel, 2:8=ethyl acetate:hexanes) gave (S)-tert-butyl 4-((R)-4-ethoxy-4-oxobutan-2-yl)-2,2-dimethyloxazolidine-3-carboxylate as a clear oil.

後処理

  1. extractionThe mixture was extracted with ether
  2. washwashed with brine
  3. dry with materialdried over sodium sulfate
  4. concentrationconcentrated

出典と根拠

ORDレコード
ord-7d8d6197b34c466986f01dabcd3cfa73
出典データセット
uspto-grants-2007_12
特許番号
US07312218B2

関連ノート

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