Triphenylphosphine → 5-Ethoxycarbonylmethylene-7-fluoro-1-oxo-1,3,4,5-tetrahydro-azepino[3,4-b]indole-2,10-dicarboxylic acid di-tert-butyl ester

HRID 29787노트

반응식

HRID 29787 반응식
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:20]([O:24][C:25]([N:27]1[C:35]2[C:30](=[CH:31][C:32]([F:36])=[CH:33][CH:34]=2)[C:29](I)=[C:28]1[C:38]([N:40]([C:50]([O:52][C:53]([CH3:56])([CH3:55])[CH3:54])=[O:51])[CH2:41][CH2:42][CH:43]=[CH:44][C:45]([O:47][CH2:48][CH3:49])=[O:46])=[O:39])=[O:26])([CH3:23])([CH3:22])[CH3:21]>C1COCC1.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:53]([O:52][C:50]([N:40]1[CH2:41][CH2:42][C:43](=[CH:44][C:45]([O:47][CH2:48][CH3:49])=[O:46])[C:29]2[C:30]3[C:35](=[CH:34][CH:33]=[C:32]([F:36])[CH:31]=3)[N:27]([C:25]([O:24][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:26])[C:28]=2[C:38]1=[O:39])=[O:51])([CH3:55])([CH3:56])[CH3:54]

참가 물질

5

반응물 2

HCID 11776TriphenylphosphineHCID 686374172-[Tert-butoxycarbonyl-(4-ethoxycarbonyl-but-3-enyl)-aminocarbonyl]-5-fluoro-3-iodo-indole-1-carboxylic acid tert-butyl ester

생성물 1

HCID 686390865-Ethoxycarbonylmethylene-7-fluoro-1-oxo-1,3,4,5-tetrahydro-azepino[3,4-b]indole-2,10-dicarboxylic acid di-tert-butyl ester

시약·촉매·용매 2

HCID 167845palladium(II) acetate촉매HCID 8028Tetrahydrofuran용매2회

실험 절차

A suspension of triphenylphosphine (3.36 g, 12.8 mmol), Pd(OAc)2 (1.44 g, 6.40 mmol) and Ag2CO3 (3.53 g, 12.8 mmol) in anhydrous THF (100 mL) is stirred at room temperature for 15 minutes. A solution of 2-[tert-butoxycarbonyl-(4-ethoxycarbonyl-but-3-enyl)-aminocarbonyl]-5-fluoro-3-iodo-indole-1-carboxylic acid tert-butyl ester (4.03 g, 6.40 mmol), prepared as in reference 15, in THF (10 mL) is added to the above prepared suspension. The mixture is heated at 60° C. for 16 hours. The inorganic precipitate is removed and the organic layer is concentrated. The residue is purified by silica gel column chromatography and eluted with EtOAc-Hexanes to give the 5-ethoxycarbonylmethylene-7-fluoro-1-oxo-1,3,4,5-tetrahydro-azepino[3,4-b]indole-2,10-dicarboxylic acid di-tert-butyl ester; 1H NMR (CDCl3) δ 1.34 (t, 3H, J=7.6 Hz), 1.57 (s, 9H), 1.60 (s, 9H), 3.46-3.52 (m, 2H), 4.13 (t, 2H, J=4.8 Hz), 4.24 (q, 2H, J=7.6 Hz), 6.30 (t, 1H, J=2.8 Hz), 7.21 (td, 1H, J1=2.8 Hz, J2=9.2 Hz), 7.42 (dd, 1H, J1=2.8 Hz, J2=8.8 Hz), 8.10 (dd, 1H, J1=4.0 Hz, J2=9.2 Hz); m/z [M++Na] 525.0.

후처리

  1. temperatureThe mixture is heated at 60° C. for 16 hours
  2. customThe inorganic precipitate is removed
  3. concentrationthe organic layer is concentrated
  4. customThe residue is purified by silica gel column chromatography
  5. washeluted with EtOAc-Hexanes

출처 및 근거

ORD 기록
ord-4c0c4def8b8746c0826f702cdf2d481d
출처 데이터셋
uspto-grants-2008_09
특허 번호
US07423031B2

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