3-(Dimethylamino)acrylaldehyde → Tert-butyl 3-(1,1-dimethylethylsulfinamido)-3-(pyrimidin-2-yl)azetidine-1-carboxylate

HRID 509558Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 509558
[C:1]([C:4]1([NH:15][S:16]([C:18]([CH3:21])([CH3:20])[CH3:19])=[O:17])[CH2:7][N:6]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:5]1)(=[NH:3])[NH2:2].C[O-].[Na+].CN(C)/[CH:27]=[CH:28]/[CH:29]=O>CO>[CH3:19][C:18]([CH3:21])([S:16]([NH:15][C:4]1([C:1]2[N:2]=[CH:29][CH:28]=[CH:27][N:3]=2)[CH2:5][N:6]([C:8]([O:10][C:11]([CH3:13])([CH3:14])[CH3:12])=[O:9])[CH2:7]1)=[O:17])[CH3:20]

Komponenten

5

Edukt 3

HCID 6383203-(Dimethylamino)acrylaldehydeHCID 10942334Sodium MethoxideHCID 89835483Tert-butyl 3-carbamimidoyl-3-(1,1-dimethylethylsulfinamido)azetidine-1-carboxylate

Produkt 1

HCID 89825281Tert-butyl 3-(1,1-dimethylethylsulfinamido)-3-(pyrimidin-2-yl)azetidine-1-carboxylateAusbeute 12 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

To the above reaction mixture of tert-butyl 3-carbamimidoyl-3-(1,1-dimethylethylsulfinamido)azetidine-1-carboxylate (assumed 4.98 mmol) in methanol (5 mL) was added sodium methoxide (0.509 g, 9.42 mmol) and (E)-3-(dimethylamino)acrylaldehyde (0.560 g, 5.65 mmol), and the resulting solution was heated at 70° C. overnight. The reaction mixture was then concentrated and the residue dissolved in ethyl acetate. The mixture was washed with water followed by saturated brine solution, and then dried over Na2SO4 and concentrated. The crude product was then purified by column chromatography (50% EtOAc in Hexane) to afford tert-butyl 3-(1,1-dimethylethylsulfinamido)-3-(pyrimidin-2-yl)azetidine-1-carboxylate Yield: 200 mg (overall 12%). 1H NMR (400 MHz, CDCl3): δ 8.78 (d, J=4.8 Hz, 2H), 7.24 (m, 1H), 4.63-4.48 (m, 2H), 4.23 (d, J=9.2 Hz, 2H), 1.47 (s, 9H), 1.29 (s, 9H). LCMS: (ES+) m/z observed=255.2 (M+H)+ of 2-methyl-N-(3-(pyrimidin-2-yl)azetidin-3-yl)propane-2-sulfinamide.

Aufarbeitung

  1. concentrationThe reaction mixture was then concentrated
  2. dissolutionthe residue dissolved in ethyl acetate
  3. washThe mixture was washed with water
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated
  6. customThe crude product was then purified by column chromatography (50% EtOAc in Hexane)

Quellen und Nachweise

ORD-Eintrag
ord-ee5e53443b2e4feb84c6ce9a579fc8c4
Quelldatensatz
uspto-grants-2015_08
Patentnummer
US09096580B2

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