Triethylamine → (9S,13S)-15-benzyl 13,9-di-tert-butyl 3,11-dioxo-1-phenyl-2-oxa-4,10,12-triazapentadecane-9,13,15-tricarboxylate

HRID 1509783Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1509783
[NH2:1][C@H:2]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:3][CH2:4][C:5](=[O:14])[O:6][CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.Cl.Cl[C:24](Cl)([O:26]C(=O)OC(Cl)(Cl)Cl)Cl.C(N(CC)CC)C.[NH2:42][C@H:43]([C:59]([O:61][C:62]([CH3:65])([CH3:64])[CH3:63])=[O:60])[CH2:44][CH2:45][CH2:46][CH2:47][NH:48][C:49]([O:51][CH2:52][C:53]1[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=1)=[O:50]>ClCCCl>[O:50]=[C:49]([NH:48][CH2:47][CH2:46][CH2:45][CH2:44][C@@H:43]([C:59]([O:61][C:62]([CH3:65])([CH3:64])[CH3:63])=[O:60])[NH:42][C:24](=[O:26])[NH:1][C@H:2]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:3][CH2:4][C:5]([O:6][CH2:7][C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1)=[O:14])[O:51][CH2:52][C:53]1[CH:54]=[CH:55][CH:56]=[CH:57][CH:58]=1

Komponenten

6

Edukt 4

HCID 8471TriethylamineHCID 94429TriphosgeneHCID 1581102N6-[(Phenylmethoxy)carbonyl]-L-lysine 1,1-dimethylethyl esterHCID 56777356L-Glutamic acid alpha-t-butyl-delta-benzyl ester hydrochloride

Produkt 1

HCID 59404356(9S,13S)-15-benzyl 13,9-di-tert-butyl 3,11-dioxo-1-phenyl-2-oxa-4,10,12-triazapentadecane-9,13,15-tricarboxylateAusbeute 229,5 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 111,2-DichloroethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

To a solution of L-Glu(OBn)-OtBu hydrochloride (3.13 mg, 9.49 mmol) and triphosgene (923 mg, 3.13 mmol) in DCE (70 mL) cooled to −78° C. was added triethylamine (2.80 mL) under nitrogen. After stirring at −78° C. for 2 h, a solution of L-Lys(Z)-OtBu (3.88 g, 10.40 mmol) and TEA (1.5 mL) in DCE (10 mL) was added. The mixture was allowed to come to room temperature over a period of 1 h and stirred at room temperature overnight. The reaction was quenched with 1N HCl, and extracted with DCM. The organic layer was dried and concentrated under reduced pressure and the residue was purified utilizing a Biotage SP4 to afford (9S,13S)-15-benzyl 13,9-di-tert-butyl 3,11-dioxo-1-phenyl-2-oxa-4,10,12-triazapentadecane-9,13,15-tricarboxylate as a colorless oil (4.71 g, 76%). 1H NMR (400 MHz, CDCl3) δ 7.34-7.29 (m, 10H), 5.13-5.04 (m, 6H), 4.97 (brs, 1H), 4.38-4.28 (m, 2H), 3.18-3.14 (m, 2H), 2.50-2.35 (m, 2H), 2.19-2.10 (m, 1H), 1.94-1.85 (m, 1H), 1.79-1.72 (m, 1H), 1.58-1.33 (m, 21H).

Aufarbeitung

  1. waitto come to room temperature over a period of 1 h
  2. stirringstirred at room temperature overnight
  3. customThe reaction was quenched with 1N HCl
  4. extractionextracted with DCM
  5. customThe organic layer was dried
  6. concentrationconcentrated under reduced pressure
  7. customthe residue was purified

Quellen und Nachweise

ORD-Eintrag
ord-0636f40ae1b846aa92185b81c9594483
Quelldatensatz
uspto-grants-2012_07
Patentnummer
US08211402B2

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