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Acetoacetic Acid → (11s,11As)-7,8-dimethoxy-2-oxo-11-(tert-butyldimethylsilyloxymethyl)-10-(2,2,2-trichloroethoxycarbonyl)-1,2,3,10,11,11a-hexahydro-5h-pyrrolo [2,1-c][1,4]benzodiazepin-5-one

HRID 18866
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Reaktionsgleichung

Reaktionsgleichung von HRID 18866
CC(CC(O)=O)=O.N=O.CC1(C)CCCC(C)(C)N1.[CH3:20][O:21][C:22]1[C:23]([O:55][CH3:56])=[CH:24][C:25]2[N:31]([C:32]([O:34][CH2:35][C:36]([Cl:39])([Cl:38])[Cl:37])=[O:33])[C@H:30]([CH2:40][O:41][Si:42]([C:45]([CH3:48])([CH3:47])[CH3:46])([CH3:44])[CH3:43])[C@@H:29]3[CH2:49][C@@H:50]([OH:52])[CH2:51][N:28]3[C:27](=[O:53])[C:26]=2[CH:54]=1>C(Cl)Cl>[CH3:20][O:21][C:22]1[C:23]([O:55][CH3:56])=[CH:24][C:25]2[N:31]([C:32]([O:34][CH2:35][C:36]([Cl:39])([Cl:37])[Cl:38])=[O:33])[C@H:30]([CH2:40][O:41][Si:42]([C:45]([CH3:48])([CH3:47])[CH3:46])([CH3:44])[CH3:43])[C@@H:29]3[CH2:49][C:50](=[O:52])[CH2:51][N:28]3[C:27](=[O:53])[C:26]=2[CH:54]=1
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Komponenten

5

Edukt 3

HCID 96Acetoacetic AcidHCID 66670125(11s,11As,2r)-7,8-dimethoxy-2-hydroxy-11-(tert-butyldimethylsilyloxymethyl)-10-(2,2,2-trichloroethoxycarbonyl)-1,2,3,10,11,11a-hexahydro-5h-pyrrolo[2,1-c][1,4]benzodiazepin-5-oneHCID 666701942,2,6,6-Tetramethylpiperidine nitroxyl

Produkt 1

HCID 66670095(11s,11As)-7,8-dimethoxy-2-oxo-11-(tert-butyldimethylsilyloxymethyl)-10-(2,2,2-trichloroethoxycarbonyl)-1,2,3,10,11,11a-hexahydro-5h-pyrrolo [2,1-c][1,4]benzodiazepin-5-one

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

Diodobenzene diacetate (2.44 g, 7.58 mmol, 1.78 Equiv.) and 2,2,6,6-tetramethylpiperidine nitroxyl (TEMPO) (133 mg, 0.85 mmol, 0.2 Equiv.) were added to a stirred solution of 25 (2.49 g, 4.26 mmol; 1.0 Equiv.) in dry DCM (40 mL). The mixture was stirred at room temperature for 18 h and the reaction mixture was diluted with DAM (50 mL). The organic phase was washed with said sodium bisulphite (2×25 mL), brine (40 mL), dried (MgSO4) and concentrated in vacuo. Purification by flash chromatography (EtOAc/Petroleum ether 6:4) afforded 26 as a white glass. (2.26 g, 91%): [α]D22=+95.0° (c=0.795, CHCl3); 1H NMR (CDCl3, 500 MHz) δ 0.22, 0.23 (two s, 6H, Si(CH3)2), 0.86 (s, 9H, C(CH3)3), 2.56 (dd, 1H, J=3.12, 19.60, H1b), 2.96 (dd, 1H, J=10.29, 18.9, H1a), 3.90 (s, 3H, CH3O8), 3.95-3.99 (m, 5H, H3b, H11a and CH3O7), 4.21 (d, 1H, J=12.02 Hz, Cl3CCH2), 4.32 (d, 1H, J=20.93 Hz, H3a), 5.24 (d, 1H, J=12.03 Hz, Cl3CCH2), 5.83 (d, 1H, J=9.26 Hz, H11), 6.77 (s, 1H, H9), 7.25 (s, 1H, H6); 13C NMR (CDCl3, 125 MHz) δ 207.8 (C2), 168.0 (C5), 153.7 (OC═ONH), 151.4 (C8), 149.2 (C7), 128.0 (C9-10), 124.5 (C5-6), 113.0 (C9), 110.4 (C6), 95.1 (Cl3C), 87.4 (C11), 74.8 (Cl3CCH2), 58.9 (C11a), 56.2 (CH3O7), 56.0 (CH3O8), 52.8 (C3), 40.3 (C1), 25.5 (C(CH3)3), 17.8 (Cquat), −4.2 and −5.3 (Si(CH3)2); IR (film) 2934, 1763 (C═O), 1720 (OC═ON), 1649 (NC═O), 1604, 1515, 1402, 1274, 1217, 1120, 1075, 1002, 866, 834, 756, 712 cm−1; MS (EI) m/z (relative intensity) 615 ([M+MeOH]+., 100).

Aufarbeitung

  1. additionthe reaction mixture was diluted with DAM (50 mL)
  2. washThe organic phase was washed
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customPurification by flash chromatography (EtOAc/Petroleum ether 6:4)

Quellen und Nachweise

ORD-Eintrag
ord-e4b0550c05b740be88099225c8cb6006
Quelldatensatz
uspto-grants-2010_06
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US07741319B2

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