tert-Butyl 2-(methoxy(methyl)amino)-1-methyl-2-oxoethylcarbamate → (S)-tert-butyl 3-oxo-4-(pyridin-2-yl)butan-2-ylcarbamate

HRID 473442

Reaktionsgleichung

Reaktionsgleichung von HRID 473442
CON(C)[C:4](=[O:15])[CH:5]([NH:7][C:8](=[O:14])[O:9][C:10]([CH3:13])([CH3:12])[CH3:11])[CH3:6].C(=O)=O.C(#N)C.C([Mg]Cl)(C)C.Br[Mg][CH2:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][N:32]=1>C1COCC1>[O:15]=[C:4]([CH2:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][N:32]=1)[C@@H:5]([NH:7][C:8](=[O:14])[O:9][C:10]([CH3:11])([CH3:12])[CH3:13])[CH3:6]

Komponenten

6

Edukt 4

HCID 375613tert-Butyl 2-(methoxy(methyl)amino)-1-methyl-2-oxoethylcarbamateHCID 86587134Acetonitrile dry iceHCID 178418918HCID 178418918, VerbindungHCID 178419667HCID 178419667, Verbindung

Produkt 1

HCID 58318617(S)-tert-butyl 3-oxo-4-(pyridin-2-yl)butan-2-ylcarbamate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

tert-Butyl 1-(methoxy(methyl)amino)-1-oxopropan-2-ylcarbamate (50.0 g, 215 mmol) in THF (450 mL) was cooled to −40° C. (dry ice/acetonitrile) and slowly charged with isopropylmagnesium chloride (2.0M, 102.2 mL, 0.95 eq). After a clear solution was obtained (became clear at −20° C. and milky again at −40° C.), bromo(pyridin-2-ylmethyl)magnesium solution (see below for preparation) was added drop wise using cannula before warming to rt overnight. The reaction mixture was quenched with NH4Cl solution and extracted with EtOAc (500 mL×2). The combined organic layers were washed with water, brine, dried over sodium sulfate, and concentrated under high vacuum to give (S)-tert-butyl 3-oxo-4-(pyridin-2-yl)butan-2-ylcarbamate as a tan oil. Small scale reaction was purified by combiflash (EtOAc/hexane, up to 1/3) to give a red oil. Mass Spectrum (ESI) m/e=265 (M+1).

Aufarbeitung

  1. customAfter a clear solution was obtained (
  2. custombecame clear at −20° C.
  3. customThe reaction mixture was quenched with NH4Cl solution
  4. extractionextracted with EtOAc (500 mL×2)
  5. washThe combined organic layers were washed with water, brine
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated under high vacuum

Quellen und Nachweise

ORD-Eintrag
ord-6dfe5724be4149c79381fa186e91e7bf
Quelldatensatz
uspto-grants-2014_01
Patentnummer
US08633313B2

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