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

HRID 1525337노트

반응식

HRID 1525337 반응식
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]

참가 물질

7

반응물 3

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

생성물 1

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

시약·촉매·용매 3

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

반응 조건

온도
80 °C

실험 절차

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]+.

후처리

  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)

출처 및 근거

ORD 기록
ord-0c0335406a8d4591b41d460b8d9b2552
출처 데이터셋
uspto-grants-2015_07
특허 번호
US09079930B2

반응 노트

불러오는 중…