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Trifluoroacetic acid → 5-{(9aS)-3-(ethoxycarbonyl)-2-[2-(4-fluorophenyl)ethyl]-5-oxo-7,8,9,9a-tetrahydro-5H-pyrido[2,3-a]pyrrolizin-4-yl}-3-furoic acid

HRID 458418
ノート
印刷プレビュー

反応式

HRID 458418 の反応式
C(O[C:4](=O)[CH2:5][C:6]([C@@H:8]1[CH2:12][CH2:11][CH2:10][N:9]1[C:13]([O:15]C(C)(C)C)=O)=O)C.C([C:23]1[O:27][CH:26]=[C:25]([C:28]([OH:30])=[O:29])[CH:24]=1)=O.N1CCCCC1.[NH2:37]/[C:38](/[CH2:45][CH2:46][C:47]1[CH:52]=[CH:51][C:50]([F:53])=[CH:49][CH:48]=1)=[CH:39]\[C:40]([O:42][CH2:43][CH3:44])=[O:41].C(O)(C(F)(F)F)=O>CCOCC.CC#N.CO.CCOC(C)=O.O.CN(C=O)C>[CH2:43]([O:42][C:40]([C:39]1[C:38]([CH2:45][CH2:46][C:47]2[CH:48]=[CH:49][C:50]([F:53])=[CH:51][CH:52]=2)=[N:37][C:6]2[C@H:8]3[N:9]([C:13](=[O:15])[C:5]=2[C:4]=1[C:23]1[O:27][CH:26]=[C:25]([C:28]([OH:30])=[O:29])[CH:24]=1)[CH2:10][CH2:11][CH2:12]3)=[O:41])[CH3:44]
参加物実験手順後処理出典と根拠反応ノート

参加物

12

反応物 5

HCID 6422Trifluoroacetic acidHCID 8082PiperidineHCID 18441995ethyl (Z)-3-amino-5-(4-fluorophenyl)pent-2-enoateHCID 223237835-Formylfuran-3-carboxylic acidHCID 57407385(S)-1-Boc-2-(3-ethoxy-3-oxopropanoyl)pyrrolidine

生成物 1

HCID 69516584
5-{(9aS)-3-(ethoxycarbonyl)-2-[2-(4-fluorophenyl)ethyl]-5-oxo-7,8,9,9a-tetrahydro-5H-pyrido[2,3-a]pyrrolizin-4-yl}-3-furoic acid
収率 43.1%

試薬・触媒・溶媒 6

HCID 887Methanol溶媒HCID 962Water溶媒HCID 3283Diethyl Ether溶媒2 回HCID 6228Dimethylformamide溶媒HCID 6342Acetonitrile溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A DMF (10 mL) solution of tert-Butyl (2S)-2-(3-ethoxy-3-oxopropanoyl)-1-pyrrolidinecarboxylate (2.85 g, 9.99 mmol), 5-formyl-3-furoic acid (1.40 g, 9.99 mmol) and piperidine (0.494 mL, 5.00 mmol) was heated to 80° C. for 45 min and then cooled to ambient temperature. The reaction mixture was diluted with Et2O and washed 1 N HCl, 2× H2O, 1× brine and the organics dried (Na2SO4), filtered and concentrated to a brown residue. The Knoevenagel product (4.07 g, 9.99 mmol) and ethyl (2Z)-3-amino-5-(4-fluorophenyl)-2-pentenoate (2.37 g, 9.99 mmol) were heated to 110° C. for 1.5 h and then cooled to ambient temperature. The glassy solid was redissolved in CH3CN (20 mL) and H2O (20 mL) followed by addition of ceric ammonium nitrate (10.95 g, 19.98 mmol). The reaction mixture stirred for 45 min at ambient temperature and then Et2O was added and the organics extracted and washed 1× H2O, 1× brine, and then dried (Na2SO4), filtered and concentrated to a dark tan solid. The solid from the previous reaction was subjected to TFA (15 mL in 4 mL CH2Cl2) for 1 h and then concentrated. The residue was redissolved in CH2Cl2 (20 mL) and treated with Et3N (12 mL). After 16 h the reaction mixture was concentrated to a brown foam. The residue was redissolved in CHCl3 and washed 1× pH 4.5 buffer, 1× brine and the organics dried (Na2SO4), filtered and concentrated. Chromatography on silica gel using 9:1 EtOAc:MeOH eluted the desired compound as a tan solid (2.06 g, 4.31 mmol) 43% yield: 1H NMR (CDCl3, 400 MHz) δ 8.17 (s, 1H), 8.07 (s, 1H), 7.21 (dd, J=8.6, 5.5 Hz, 2H), 6.99 (t, J=8.6 Hz, 2H), 4.73 (dd, J=10.2, 6.1 Hz, 1H), 4.37 (dd, J=10.6, 7.2 Hz, 2H), 3.88–3.76 (m, 1H), 3.47–3.42 (m, 1H), 3.17–3.03 (m, 4H), 2.48–2.32 (m, 3H), 1.42–1.34 (m, 1H), 1.26 (t, J=7.2 Hz, 3H); ESMS m/z 479 (M+H)+, 477 (M−H)+

後処理

  1. washwashed 1 N HCl, 2× H2O, 1× brine
  2. dry with materialthe organics dried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated to a brown residue
  5. temperaturecooled to ambient temperature
  6. extractionthe organics extracted
  7. washwashed 1× H2O, 1× brine
  8. dry with materialdried (Na2SO4)
  9. filtrationfiltered
  10. concentrationconcentrated to a dark tan solid
  11. customThe solid from the previous reaction
  12. concentrationconcentrated
  13. dissolutionThe residue was redissolved in CH2Cl2 (20 mL)
  14. additiontreated with Et3N (12 mL)
  15. concentrationAfter 16 h the reaction mixture was concentrated to a brown foam
  16. dissolutionThe residue was redissolved in CHCl3
  17. washwashed 1× pH 4.5 buffer
  18. dry with material1× brine and the organics dried (Na2SO4)
  19. filtrationfiltered
  20. concentrationconcentrated

出典と根拠

ORDレコード
ord-686d1da6ec0647148299450124e6a711
出典データセット
uspto-grants-2007_03
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07189851B2

反応ノート

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