(2S,4R)-1-allyloxycarbonyl-2-t-butyldimethylsilyloxymethyl-4-hydroxypyrrolidine → (3R,5S)-5-(((tert-Butyldimethylsilyl)oxy)methyl)pyrrolidin-3-ol

HRID 915712Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 915712
C(OC([N:11]1[CH2:15][C@H:14]([OH:16])[CH2:13][C@H:12]1[CH2:17][O:18][Si:19]([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:21])[CH3:20])=O)C1C=CC=CC=1.O[C@H]1[C@@H]2CC(=C)CN2C(=O)C2C=C(I)C=CC=2N1NC(OCC(Cl)(Cl)Cl)=O.C(OC(N1C[C@H](O)C[C@H]1CO[Si](C(C)(C)C)(C)C)=O)C=C>C(OCC)(=O)C.C(O)C.[Pd]>[Si:19]([O:18][CH2:17][C@@H:12]1[CH2:13][C@@H:14]([OH:16])[CH2:15][NH:11]1)([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:21])[CH3:20]

Komponenten

7

Edukt 3

HCID 18639173(2S,4R)-1-allyloxycarbonyl-2-t-butyldimethylsilyloxymethyl-4-hydroxypyrrolidineHCID 57280098benzyl (2S,4R)-2-{[(tert-butyldimethylsilyl)oxy]methyl}-4-hydroxypyrrolidine-1-carboxylateHCID 69462904(11S,11aS)-11-Hydroxy-7-iodo-2-methylidene-10-(2,2,2-trichloroethyloxycarbonylamino)-1,2,3,10,11,11a-hexahydro-5H-pyrrolo[2,1-c][1,4]benzodiazepin-5-one

Produkt 1

HCID 11481662(3R,5S)-5-(((tert-Butyldimethylsilyl)oxy)methyl)pyrrolidin-3-ol

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 23938PalladiumKatalysatorHCID 702EthanolLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

A slurry of 10% Pd/C (190 mg) in ethyl acetate (20 mL) was added to a solution of TBDMS ether (43) (1.90 g, 5.19 mmol) in ethanol (100 mL). The reaction mixture was hydrogenated (Parr apparatus) for 16 h. The catalyst was removed by vacuum filtration through Celite and excess solvent was evaporated under reduced pressure to give a yellow oil in quantitative yield (1.20 g, 100%). [α]22.2D=+35.6° (c 0.042,CHCl3). 1H NMR (CDCl3): δ −(0.07-0.08) (m, 6H, H1=, H2=), 0.82 (s, 9H, H3=, H4=, H5=), 1.68-1.73 (m, 2H, H1,), 2.99-3.11 (m, 2H, H11), 3.47-3.50 (m, 3H, H11a, H3), 4.09 (bs, 1H, NH or OH), 4.32 (bs, 1H, NH or OH). 13C NMR (CDCl3): δ −5.4 (C3=, C5=, C6=), 18.1 (C4=), 25.8 (C1=, C2=), 37.4 (C1), 54.6 (C11), 58.1 (C2), 64.6 (C3), 72.2 (C11a). IR (thin film): v=3330 (OH), 2928, 2857, 1557, 1421, 1331 (C—CH3), 1249 (CH3-Si), 1204 (t-Bu), 1191 (t-Bu), 1100 (Si—O), 1073, 993, 713 cm−1. MS (Cl) m/e (relative intensity): 232 (M+., 100), 230 (13), 174 (5), 133 (6), 86 (6).

Aufarbeitung

  1. customfor 16 h
  2. customThe catalyst was removed by vacuum filtration through Celite and excess solvent
  3. customwas evaporated under reduced pressure
  4. customto give a yellow oil in quantitative yield (1.20 g, 100%)

Quellen und Nachweise

ORD-Eintrag
ord-0ea49f68c518412cae3c8e35ef233846
Quelldatensatz
uspto-grants-2007_09
Patentnummer
US07265105B2

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