Triethylamine → Methyl 2-(methoxymethylene)-4-(trimethylsilyl)but-3-ynoate

HRID 1525337ノート

反応式

HRID 1525337 の反応式
I[C:2](=[CH:7][O:8][CH3:9])[C:3]([O:5][CH3:6])=[O:4].[C:10]([Si:12]([CH3:15])([CH3:14])[CH3:13])#[CH:11].C(N(CC)CC)C>CN(C=O)C.[Cu]I.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:9][O:8][CH:7]=[C:2]([C:11]#[C:10][Si:12]([CH3:15])([CH3:14])[CH3:13])[C:3]([O:5][CH3:6])=[O:4]

参加物

7

反応物 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 54067316Methyl 2-iodo-3-methoxyprop-2-enoate

生成物 1

HCID 53914070Methyl 2-(methoxymethylene)-4-(trimethylsilyl)but-3-ynoate収率 57%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
80 °C

実験手順

A mixture of compound 37-g (30 g, 124 mmol), ethynyltrimethylsilane (24.3 g, 248 mmol), triethylamine (37.6 g, 372 mmol), copper(I) iodide (2.35 g, 6.2 mmol), Pd(dppf)Cl2 (2.50 g) in DMF (300 mL) was stirred overnight at 80° C. The reaction mixture was cooled to room temperature, poured into ice-water, and extracted with ethyl acetate. The organic layer was washed with water, brine, and dried over sodium sulfate and concentrated. The residue was purified by flash chromatography (PE:EA=1:5) to afford compound 37-h (15 g, 57%) as a yellow solid. 1H NMR (300 MHz, CDCl3) δ 7.671 (s, 1H), 3.977 (s, 3H), 3.763 (s, 3H), 0.234 (s, 9H); LC-MS (ESI): 213 [M+H]+.

後処理

  1. temperatureThe reaction mixture was cooled to room temperature
  2. extractionextracted with ethyl acetate
  3. washThe organic layer was washed with water, brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified by flash chromatography (PE:EA=1:5)

出典と根拠

ORDレコード
ord-0c0335406a8d4591b41d460b8d9b2552
出典データセット
uspto-grants-2015_07
特許番号
US09079930B2

反応ノート

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