tert-Butanol → {1-[3-(tert-Butyldimethylsilyloxy)propyl]-1H-indol-4-yl}acetonitrile

HRID 751503

반응식

HRID 751503 반응식
[Si:1]([O:8][CH2:9][CH2:10][CH2:11][N:12]1[C:20]2[CH:19]=[CH:18][CH:17]=[C:16]([CH:21]=O)[C:15]=2[CH:14]=[CH:13]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].O1CCCC1.[C-]#N.[Li+].[C:31](P(=O)(OCC)OCC)#[N:32].CC(O)(C)C.[I-].[Sm+2].[I-]>O1CCCC1>[Si:1]([O:8][CH2:9][CH2:10][CH2:11][N:12]1[C:20]2[C:15](=[C:16]([CH2:21][C:31]#[N:32])[CH:17]=[CH:18][CH:19]=2)[CH:14]=[CH:13]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

참가 물질

7

반응물 5

HCID 6386tert-ButanolHCID 76257Diethyl cyanophosphonateHCID 179854761-[3-(tert-Butyldimethylsilyloxy)propyl]-1H-indole-4-carboxaldehydeHCID 86597616Lithium cyanide tetrahydrofuranHCID 178506586HCID 178506586, 화합물2회

생성물 1

HCID 17985901{1-[3-(tert-Butyldimethylsilyloxy)propyl]-1H-indol-4-yl}acetonitrile수율 84%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

Add 1-[3-(tert-Butyldimethylsilyloxy)propyl]-1H-indole-4-carboxaldehyde (2.34 g, 14.4 mmol) and lithium cyanide tetrahydrofuran complex (LiCN*1.5 THF, 204 mg, 1.44 mmol) to tetrahydrofuran (40 mL) under nitrogen. Add dropwise neat diethyl cyanophosphonate (2.8 mL, 18.4 mmol) to the stirring reaction mixture. Stir at room temp under nitrogen for 60 hours. Add 2-methyl-2-propanol (1.4 mL, 14.6 mmol). Add the reaction mixture via cannula to a stirred 0.1 molar solution of samarium(II) iodide in tetrahydrofuran (360 mL, 36.0 mmol) at 25° C. under nitrogen. If the resulting reaction mixture is not deep blue add additional samarium(II) iodide solution until deep blue color persists. Stir the reaction at 25° C. for 1 hour. Concentrate under reduced pressure, dilute with ethyl acetate, diethyl ether (1:1), wash with aqueous 0.1 molar hydrochloric acid, and aqueous saturated sodium chloride. Dry the organic phase over anhydrous magnesium sulfate, filter, and concentrate under reduced pressure. Chromatograph on flash silica using a gradient from neat hexane to 25% ethyl acetate in hexane to obtain 2.1 g (84%) of the title compound as an off-white solid. 1H NMR (400 MHz, DMSO-dd) 7.43 (d, J=8 Hz, 1H), 7.38 (m, 1H), 7.14 (m, 1H), 7.0 (d, J=8 Hz, 1H), 6.54 (m, 1H), 4.23 (t, J=7, 2H), 4.18 (s, 3H), 3.5 (t, J=7 z, 2H), 1.9 (m, 2H), 0.85 (s, 9H), 0.0 (s, 6H).

후처리

  1. customto the stirring reaction mixture
  2. customIf the resulting reaction mixture
  3. stirringStir
  4. customthe reaction at 25° C. for 1 hour
  5. concentrationConcentrate under reduced pressure
  6. additiondilute with ethyl acetate, diethyl ether (1:1)
  7. washwash with aqueous 0.1 molar hydrochloric acid, and aqueous saturated sodium chloride
  8. dry with materialDry the organic phase over anhydrous magnesium sulfate
  9. filtrationfilter
  10. concentrationconcentrate under reduced pressure

출처 및 근거

ORD 기록
ord-7628be49715b4c8c92bf732cb3f64f00
출처 데이터셋
uspto-grants-2008_07
특허 번호
US07405305B2

연결된 노트

불러오는 중…