Lithium Hexamethyldisilazide → t-Butyl-[2-(4,8-dimethyl-non-1-enyl)-2,5,7,8-tetramethyl-chroman-6-yloxy]-dimethylsilane

HRID 1810598ノート

反応式

HRID 1810598 の反応式
Br[CH:2]([PH3+])[CH2:3][CH:4]([CH3:11])[CH2:5][CH2:6][CH2:7][CH:8]([CH3:10])[CH3:9].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[C:23]([Si:27]([CH3:46])([CH3:45])[O:28][C:29]1[C:30]([CH3:44])=[C:31]2[C:36](=[C:37]([CH3:40])[C:38]=1[CH3:39])[O:35][C:34]([CH3:43])([CH:41]=O)[CH2:33][CH2:32]2)([CH3:26])([CH3:25])[CH3:24]>C1COCC1>[C:23]([Si:27]([O:28][C:29]1[C:30]([CH3:44])=[C:31]2[C:36](=[C:37]([CH3:40])[C:38]=1[CH3:39])[O:35][C:34]([CH:41]=[CH:2][CH2:3][CH:4]([CH3:11])[CH2:5][CH2:6][CH2:7][CH:8]([CH3:10])[CH3:9])([CH3:43])[CH2:33][CH2:32]2)([CH3:46])[CH3:45])([CH3:24])([CH3:26])[CH3:25]

参加物

5

反応物 3

HCID 2733832Lithium HexamethyldisilazideHCID 749761846-(t-Butyl-dimethyl-silyloxy)-2,5,7,8-tetramethyl-chroman-2-carbaldehydeHCID 866467961-Bromo-3,7-dimethyl octanyl phosphonium

生成物 1

HCID 66752470t-Butyl-[2-(4,8-dimethyl-non-1-enyl)-2,5,7,8-tetramethyl-chroman-6-yloxy]-dimethylsilane収率 80%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
0 °C

実験手順

To a suspension of 1-bromo-3,7-dimethyl octanyl phosphonium (1.05 mmol) in 20 mL of anhydrous THF at 0° C. was added 1.05 mL of 1 M lithium bis(trimethysilyl)amide in THF. The mixture was stirred at 0° C. for 30 min, and compound iii (1 mmol) in 10 mL of THF was slowly added over a period of 1 h. After being stirred at room temperature for 1 h, the solution was concentrated, diluted with 20 mL of ethyl acetate, and washed, in tandem, with H2O and brine. The residue was purified by flash silica gel chromatography to afford t-butyl-[2-(4,8-dimethyl-non-1-enyl)-2,5,7,8-tetramethyl-chroman-6-yloxy]-dimethylsilane (iv) as colorless oil in 80% yield. 1H NMR (300 MHz, CDCl3) δ 0.11 (s, 6H), 0.86-0.95 (m, 6H), 1.04 (s, 9H), 1.39 (s, 1H), 1.49-1.56 (m, 1H), 1.76-1.86 (m, 1H), 2.01-2.06 (m, 2H), 2.11 (s, 3H), 2.17 (s, 6H), 2.25-2.32 (m, 1H), 2.62 (t, J=6.60 Hz, 2H), 5.30-5.44 (m, 2H).

後処理

  1. stirringAfter being stirred at room temperature for 1 h
  2. concentrationthe solution was concentrated
  3. additiondiluted with 20 mL of ethyl acetate
  4. washwashed, in tandem, with H2O and brine
  5. customThe residue was purified by flash silica gel chromatography

出典と根拠

ORDレコード
ord-d9009274bb274d37825afc5d16d0bffc
出典データセット
uspto-grants-2013_01
特許番号
US08362071B2

反応ノート

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