2-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenyl → 3-(tert-butylamino)-5-(4-oxo-4,5,6,7-tetrahydro-1H-pyrrolo[3,2-c]pyridin-2-yl)quinoxaline-2-carbaldehyde

HRID 1056169Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1056169
[C:1]([NH:5][C:6]1[C:7]([CH:25]=[O:26])=[N:8][C:9]2[C:14]([N:15]=1)=[C:13](B1OC(C)(C)C(C)(C)O1)[CH:12]=[CH:11][CH:10]=2)([CH3:4])([CH3:3])[CH3:2].CC1(C)C(C)(C)OB([C:35]2[NH:43][C:42]3[CH2:41][CH2:40][NH:39][C:38](=[O:44])[C:37]=3[CH:36]=2)O1.CC(C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C.CO.C(Cl)Cl>O1CCOCC1.O.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]([NH:5][C:6]1[C:7]([CH:25]=[O:26])=[N:8][C:9]2[C:14]([N:15]=1)=[C:13]([C:35]1[NH:43][C:42]3[CH2:41][CH2:40][NH:39][C:38](=[O:44])[C:37]=3[CH:36]=1)[CH:12]=[CH:11][CH:10]=2)([CH3:2])([CH3:3])[CH3:4]

Komponenten

8

Edukt 4

HCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 21226129Dichloromethane methanolHCID 897834962-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-YL)-1,5,6,7-tetrahydro-4H-pyrrolo[3,2-C]pyridin-4-oneHCID 897850243-(Tert-butylamino)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinoxaline-2-carbaldehyde

Produkt 1

HCID 897835263-(tert-butylamino)-5-(4-oxo-4,5,6,7-tetrahydro-1H-pyrrolo[3,2-c]pyridin-2-yl)quinoxaline-2-carbaldehydeAusbeute 18,6 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 962WaterLösungsmittel2×HCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
105 °C

Versuchsvorschrift

A mixture of 3-(tert-butylamino)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinoxaline-2-carbaldehyde (307a) (600.0 mg, 1.18 mmol), 2-bromo-6,7-dihydro-1H-pyrrolo[3,2-c]pyridin-4(5H)-one (608) (407 mg, 1.89 mmol), K2PO4 (753 mg, 3.55 mmol), X-Phos (Strem Chemicals, Inc., 56.4 mg, 0.12 mmol), and Pd2dba3 (Aldrich, 54.1 mg, 0.06 mmol) in a mixture of 1,4-dioxane (10 mL) and water (2.0 mL) was heated under argon at 105° C. for 1 h. The reaction mixture was cooled to RT, diluted with water (30 mL), and extracted with 5% MeOH/DCM (3×30 mL). The combined extracts were dried over Na2SO4, filtered, and concentrated onto silica gel. Chromatographic purification (silica gel, 0-100% EtOAc/hexanes, then 0-10% MeOH/DCM) furnished 3-(tert-butylamino)-5-(4-oxo-4,5,6,7-tetrahydro-1H-pyrrolo[3,2-c]pyridin-2-yl)quinoxaline-2-carbaldehyde (79.0 mg, 0.22 mmol, 18% yield) as a dark-red solid: m/z (ESI, +ve) 364.2 (M+H)+.

Aufarbeitung

  1. temperatureThe reaction mixture was cooled to RT
  2. extractionextracted with 5% MeOH/DCM (3×30 mL)
  3. dry with materialThe combined extracts were dried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated onto silica gel
  6. customChromatographic purification (silica gel, 0-100% EtOAc/hexanes

Quellen und Nachweise

ORD-Eintrag
ord-b113a649fac049a09d01d1c6cdca4768
Quelldatensatz
uspto-grants-2016_07
Patentnummer
US09394297B2

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