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Cesium carbonate → tert-Butyl 3-(6-(Diphenylmethyleneamino)pyridin-3-yl)azetidine-1-carboxylate

HRID 626759
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 626759
[C:1]([O:5][C:6]([N:8]1[CH2:11][CH:10]([C:12]2[CH:13]=[N:14][C:15](Cl)=[CH:16][CH:17]=2)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[C:19](=[NH:32])([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:1]([O:5][C:6]([N:8]1[CH2:11][CH:10]([C:12]2[CH:13]=[N:14][C:15]([N:32]=[C:19]([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=3)=[CH:16][CH:17]=2)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

7

Edukt 4

HCID 10796Cesium carbonateHCID 136809Benzophenone imineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 57537370Tert-butyl 3-(6-chloropyridin-3-yl)azetidine-1-carboxylate

Produkt 1

HCID 86697066tert-Butyl 3-(6-(Diphenylmethyleneamino)pyridin-3-yl)azetidine-1-carboxylate
Ausbeute 70,9 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

A mixture of 3-(6-chloropyridin-3-yl)-azetidine-1-carboxylic acid tert-butyl ester (274 mg, 1.0 mmol), benzophenone imine (0.2 mL, 1.2 mmol), Pd2(dba)3 (22 mg, 0.025 mmol), Xantphos (58 mg, 0.10 mmol) and cesium carbonate (652 mg, 2.0 mmol) in dioxane (10 mL) was de-gassed and purged with nitrogen and the reaction mixture was heated at 80° C. in a sealed vial overnight. The resultant mixture was allowed to cool to room temperature, before being partitioned between ethyl acetate and water. The layers were separated and the organic layer was washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (30-40% ethyl acetate in cyclohexane) to afford the title compound as a yellow solid (293 mg, 70% yield). LCMS (Method C): RT=3.31 min, m/z: 269 [M+H+].

Aufarbeitung

  1. customwas de-gassed
  2. custompurged with nitrogen
  3. temperatureto cool to room temperature
  4. custombefore being partitioned between ethyl acetate and water
  5. customThe layers were separated
  6. washthe organic layer was washed with brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by silica gel flash chromatography (30-40% ethyl acetate in cyclohexane)

Quellen und Nachweise

ORD-Eintrag
ord-11153f9d382d4909b86a8c490072b4a1
Quelldatensatz
uspto-grants-2016_04
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US09309240B2

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