Hydrochloric Acid → (S)-4-Benzyloxy-2-{2-[benzyloxycarbonyl-(2-tert-butoxycarbonyl-ethyl)-amino]-ethylamino}-butyric acid methyl ester

HRID 655511

Reaktionsgleichung

Reaktionsgleichung von HRID 655511
[C:1]([O:5][C:6](=[O:23])[CH2:7][CH2:8][N:9]([C:13]([O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)=[O:14])[CH2:10][CH:11]=O)([CH3:4])([CH3:3])[CH3:2].[CH3:24][O:25][C:26](=[O:39])[C@@H:27]([NH2:38])[CH2:28][CH2:29][O:30][CH2:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1.Cl.C(N(CC)CC)C.B.N1C=CC=CC=1>ClCCCl.C(O)C.C(O)(=O)C>[CH3:24][O:25][C:26](=[O:39])[C@@H:27]([NH:38][CH2:11][CH2:10][N:9]([C:13]([O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)=[O:14])[CH2:8][CH2:7][C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:23])[CH2:28][CH2:29][O:30][CH2:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1

Komponenten

8

Edukt 5

HCID 313Hydrochloric Acid2×HCID 8471TriethylamineHCID 2723995Borane;pyridineHCID 66782701(S)-2-amino-4-benzyloxy-butyric acid methyl esterHCID 866381053-[Benzyloxycarbonyl-(2-oxo-ethyl)-amino]-propionic acid tert-butyl ester

Produkt 1

HCID 67074625(S)-4-Benzyloxy-2-{2-[benzyloxycarbonyl-(2-tert-butoxycarbonyl-ethyl)-amino]-ethylamino}-butyric acid methyl esterAusbeute 79 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 176Acetic AcidLösungsmittelHCID 229016121,2-Dichloroethane ethanolLösungsmittel

Versuchsvorschrift

3.71 g (11.55 mmol) of 3-[benzyloxycarbonyl-(2-oxo-ethyl)-amino]-propionic acid tert-butyl ester and 3.00 g (11.55 mmol) of (S)-2-amino-4-benzyloxy-butyric acid methyl ester; hydrochloride (intermediate 7) were dissolved in 1,2-dichloroethane/ethanol 1:1 80 ml) and treated with 1.93 ml (13.86 mmol) of triethylamine, 3.03 ml of acetic acid and 3.03 ml (24.25 mmol, 8 M in pyridine) of pyridine-borane complex (cooling with a water bath to room temperature). The reaction was stirred at room temperature over 1¼ h, then partitioned between aq. sodium hydrogencarbonate solution and diethyl ether (3×). The organic phases were washed with sat. aq. sodium hydrogencarbonate solution, 10% aq. sodium chloride solution, dried over Na2SO4 evaporated and purified by flash silica gel column (dichloromethane/n-heptane 1:1 to dichloromethane, then dichloromethane/ethyl acetate 4:1 to ethyl acetate) to yield 4.81 g (79%) of the title compound as colorless oil. MS: 529.2 (MH+).

Aufarbeitung

  1. custompartitioned between aq. sodium hydrogencarbonate solution and diethyl ether (3×)
  2. washThe organic phases were washed with sat. aq. sodium hydrogencarbonate solution, 10% aq. sodium chloride solution
  3. dry with materialdried over Na2SO4
  4. customevaporated
  5. custompurified by flash silica gel column (dichloromethane/n-heptane 1:1 to dichloromethane

Quellen und Nachweise

ORD-Eintrag
ord-c4404e775cba46c596053c702122d12a
Quelldatensatz
uspto-grants-2011_12
Patentnummer
US08071586B2

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