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Lawesson's reagent → methyl (2S)-4-[bis(2-{[(tert-butoxy)carbonyl]amino}ethyl)carbamothioyl]-2-{[(tert-butoxy) carbonyl]amino}butanoate

HRID 1923973
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Reaktionsgleichung

Reaktionsgleichung von HRID 1923973
[C:1]([O:5][C:6]([NH:8][CH2:9][CH2:10][N:11]([CH2:29][CH2:30][NH:31][C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])[C:12]([CH2:14][CH2:15][C@H:16]([NH:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[C:17]([O:19][CH3:20])=[O:18])=O)=[O:7])([CH3:4])([CH3:3])[CH3:2].COC1C=CC(P2(SP(C3C=CC(OC)=CC=3)(=S)S2)=[S:48])=CC=1>C1COCC1.CN(C1C=CN=CC=1)C>[C:1]([O:5][C:6]([NH:8][CH2:9][CH2:10][N:11]([CH2:29][CH2:30][NH:31][C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])[C:12]([CH2:14][CH2:15][C@H:16]([NH:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[C:17]([O:19][CH3:20])=[O:18])=[S:48])=[O:7])([CH3:4])([CH3:3])[CH3:2]
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Komponenten

5

Edukt 2

HCID 87949Lawesson's reagent2×HCID 59366631Methyl N2-(tert-butoxycarbonyl)-N5,N5-bis(2-((tert-butoxycarbonyl)amino)ethyl)-L-glutaminate

Produkt 1

HCID 59366732methyl (2S)-4-[bis(2-{[(tert-butoxy)carbonyl]amino}ethyl)carbamothioyl]-2-{[(tert-butoxy) carbonyl]amino}butanoateAusbeute 45,5 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 142844-(Dimethylamino)pyridine
Katalysator
HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To the solution of methyl (2S)-4-[bis(2-{[(tert-butoxy)carbonyl]amino}ethyl)carbamoyl]-2-{[(tert-butoxy)carbonyl]amino}butanoate XIV (610 mg, 1.12 mmol) in THF (10 mL) under argon was added Lawesson's reagent (680 mg, 1.68 mmol) and DMAP (13 mg, 0.11 mmol). The mixture was stirred at r.t. for 2 h and then refluxed over weekend. An additional two portions of Lawesson's reagent (900 mg, 2.24 mmol) and was added and the reaction was refluxed for another 4 h. The solvent was evaporated under reduced pressure and the crude product was purified on a silica gel column (1:6 EtOAc/hexane) to give methyl (2S)-4-[bis(2-{[(tert-butoxy)carbonyl]amino}ethyl)carbamothioyl]-2-{[(tert-butoxy)carbonyl]amino}butanoate XV (290 mg, 0.51 mmol, 45% yield). ESIMS found for C25H46N4O8S m/z 563 (M+H).

Aufarbeitung

  1. temperaturerefluxed over weekend
  2. temperaturethe reaction was refluxed for another 4 h
  3. customThe solvent was evaporated under reduced pressure
  4. customthe crude product was purified on a silica gel column (1:6 EtOAc/hexane)

Quellen und Nachweise

ORD-Eintrag
ord-958c97d2ade64a5fb392cb6788a138eb
Quelldatensatz
uspto-grants-2012_05
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08178490B2

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