Methanol → 14-tert-Butoxycarbonylamino-18-(tert-butyldimethylsilanyloxy)-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-ene-4-carboxylic acid

HRID 346968

Reaktionsgleichung

Reaktionsgleichung von HRID 346968
C([O:3][C:4]([C:6]12[CH2:24][CH:23]1[CH:22]=[CH:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16][CH:15]([NH:25][C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[C:14](=[O:33])[N:13]1[CH:9]([CH2:10][CH:11]([O:34][Si:35]([C:38]([CH3:41])([CH3:40])[CH3:39])([CH3:37])[CH3:36])[CH2:12]1)[C:8](=[O:42])[NH:7]2)=[O:5])C.C1COCC1.CO.O.[OH-].[Li+]>O>[C:29]([O:28][C:26]([NH:25][CH:15]1[C:14](=[O:33])[N:13]2[CH:9]([CH2:10][CH:11]([O:34][Si:35]([C:38]([CH3:40])([CH3:39])[CH3:41])([CH3:37])[CH3:36])[CH2:12]2)[C:8](=[O:42])[NH:7][C:6]2([C:4]([OH:5])=[O:3])[CH:23]([CH2:24]2)[CH:22]=[CH:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16]1)=[O:27])([CH3:30])([CH3:31])[CH3:32]

Komponenten

6

Edukt 4

HCID 887MethanolHCID 8028TetrahydrofuranHCID 168937Lithium hydroxide, monohydrateHCID 6733002714-Tert-butoxycarbonylamino-18-(tert-butyl-dimethyl-silanyloxy)-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-ene-4-carboxylic acid ethyl ester

Produkt 1

HCID 6732983314-tert-Butoxycarbonylamino-18-(tert-butyldimethylsilanyloxy)-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-ene-4-carboxylic acidAusbeute 84 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 962WaterLösungsmittel

Versuchsvorschrift

To a solution of 14-tert-butoxycarbonylamino-18-(tert-butyldimethylsilanyloxy)-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-ene-4-carboxylic acid ethyl ester (1.5 g, 2.47 mmoL) in a mixed solvent system of THF (4 mL), methanol (1 mL), and water (2 mL), was added powdered lithium hydroxide monohydrate (1.0 g, 50 mmoL). The light yellow slurry was stirred at rt under N2 for 4 h. The mixture was then concentrated in vacuo, and the residue partioned between ether and water. The ether phase was discarded, and the aqueous phase was treated with 1 N HCl until reaching pH 4. This acidic solution was extracted with EtOAc (3×). The combined EtOAc extracts were dried (MgSO4), and concentrated in vacuo to give 1.2 g (84%) of 14-tert-butoxycarbonylamino-18-(tert-butyl-dimethyl-silanyloxy)-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-ene-4-carboxylic acid as an off-white solid. 1H NMR (300 MHz, CD3OD) 0.12 (s, 6H), 0.89 (s, 9H), 1.23–1.64 (m, 17H), 1.70–1.87 (m, 1H), 1.90–2.49 (m, 6H), 3.70–3.80 (m, 1H), 3.83–3.90 (m, 1H), 4.28–4.36 (m, 1H), 4.47–4.55 (m, 1H), 4.65 (s, 1H), 5.30–5.39 (m, 1H), 5.53–5.62 (m, 1H). LC-MS (Method A, retention time: 3.69 min), MS m/z 580 (M++1).

Aufarbeitung

  1. concentrationThe mixture was then concentrated in vacuo
  2. additionthe aqueous phase was treated with 1 N HCl
  3. extractionThis acidic solution was extracted with EtOAc (3×)
  4. dry with materialThe combined EtOAc extracts were dried (MgSO4)
  5. concentrationconcentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-66f89b75a7d242e8a37b6a505f65d77c
Quelldatensatz
uspto-grants-2007_02
Patentnummer
US07173004B2

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