1,1-Dichloroethane → benzyl 3-(4-(ethoxycarbonyl)-2-oxo-5-phenyl-2,3-dihydro-1H-imidazol-1-yl)piperidine-1-carboxylate

HRID 1685119

Reaktionsgleichung

Reaktionsgleichung von HRID 1685119
[N+:1](=[C:3]([C:9](=O)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[C:4]([O:6][CH2:7][CH3:8])=[O:5])=[N-].[NH:17]([CH:21]1[CH2:26][CH2:25][CH2:24][N:23]([C:27]([O:29][CH2:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)=[O:28])[CH2:22]1)[C:18](N)=[O:19].ClC(Cl)C.C(O)(C(F)(F)F)=O>C1(C)C=CC=CC=1.CCCCCCCC(O)=O.CCCCCCCC(O)=O.CCCCCCCC(O)=O.CCCCCCCC(O)=O.[Rh].[Rh]>[CH2:7]([O:6][C:4]([C:3]1[NH:1][C:18](=[O:19])[N:17]([CH:21]2[CH2:26][CH2:25][CH2:24][N:23]([C:27]([O:29][CH2:30][C:31]3[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=3)=[O:28])[CH2:22]2)[C:9]=1[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:5])[CH3:8]

Komponenten

7

Edukt 4

HCID 63651,1-DichloroethaneHCID 6422Trifluoroacetic acidHCID 605325Acetic acid, benzoyldiazo-, ethyl ester2×HCID 59292389Benzyl 3-ureidopiperidine-1-carboxylate

Produkt 1

HCID 59292287benzyl 3-(4-(ethoxycarbonyl)-2-oxo-5-phenyl-2,3-dihydro-1H-imidazol-1-yl)piperidine-1-carboxylateAusbeute 43,3 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6099591Rhodium(II) Octanoate DimerKatalysatorHCID 1140TolueneLösungsmittel2×

Versuchsvorschrift

A flask containing a mixture of ethyl 2-diazo-3-oxo-3-phenylpropanoate (16C) (2.80 g, 12.84 mmol), 16B (4.45 g, 16.05 mmol) from previous step, and 128 mL of 1:1 toluene:dichloroethane was heated at 80° C. for about 10 minutes. A suspension of rhodium octanoate dimer (0.20 g, 0.26 mmol) in 25 mL toluene was added dropwise to the reaction mixture via an addition funnel. The reaction was held at 80° C. for an additional hour after the addition was completed. After the disappearance of 16C, the reaction was cooled to RT. Approximately 8 mL of TFA was then added and the reaction was allowed to stir overnight at RT. The reaction mixture was concentrated to a green oil then purified by flash chromatography on silica gel using 5% methanol/DCM to afford benzyl 3-(4-(ethoxycarbonyl)-2-oxo-5-phenyl-2,3-dihydro-1H-imidazol-1-yl)piperidine-1-carboxylate (16D) as a tan solid (2.50 g, 42%). 1H NMR (400 MHz, DMSO-d6) δ ppm 0.94 (t, J=7.07 Hz, 3H) 1.07-1.18 (m, 2H) 1.24 (br. s., 1H) 1.62-1.78 (m, 2H) 2.36-2.43 (m, 1H) 2.59-2.68 (m, 1H) 3.46-3.58 (m, 2H) 3.96 (q, J=6.91 Hz, 2H) 4.99 (s, 1H) 7.26-7.51 (m, 11H) 10.97 (s, 1H) ESI-MS: m/z 450.1 (M+H)+.

Aufarbeitung

  1. additionA flask containing
  2. additionwas added dropwise to the reaction mixture via an addition funnel
  3. waitThe reaction was held at 80° C. for an additional hour
  4. additionafter the addition
  5. concentrationThe reaction mixture was concentrated to a green oil
  6. customthen purified by flash chromatography on silica gel using 5% methanol/DCM

Quellen und Nachweise

ORD-Eintrag
ord-6b090d2a0a0841639a828ddaf63939e5
Quelldatensatz
uspto-grants-2012_04
Patentnummer
US08148367B2

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