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 29787ノート

反応式

HRID 29787 の反応式
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]

参加物

5

反応物 2

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

生成物 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

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-4c0c4def8b8746c0826f702cdf2d481d
出典データセット
uspto-grants-2008_09
特許番号
US07423031B2

反応ノート

読み込み中…