Nitrogen → HCID 67093544, Verbindung

HRID 593573Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 593573
[C:1]([N:8]1[C:16]2[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=2)[CH:10]=[C:9]1B(O)O)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[Cl:20][C:21]1[CH:22]=[N:23][CH:24]=[C:25](Br)[CH:26]=1.COC1C=CC=C(OC)C=1C1C=CC=CC=1P(C1CCCCC1)C1CCCCC1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].N#N>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].C1(C)C=CC=CC=1>[C:4]([O:3][C:1]([N:8]1[C:16]2[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=2)[CH:10]=[C:9]1[C:25]1[CH:24]=[N:23][CH:22]=[C:21]([Cl:20])[CH:26]=1)=[O:2])([CH3:7])([CH3:6])[CH3:5]

Komponenten

8

Edukt 5

HCID 947NitrogenHCID 62657Potassium Phosphate, TribasicHCID 6062563-Bromo-5-chloropyridineHCID 27733021-(tert-Butoxycarbonyl)indole-2-boronic Acid (contains varying amounts of Anhydride)HCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl

Produkt 1

HCID 67093544HCID 67093544, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 1140TolueneLösungsmittel

Versuchsvorschrift

A flask is charged with N-Boc-indole-2-boronic acid (0.407 g, 1.55 mmol), 3-chloro-5-bromopyridine (0.200 g, 1.03 mmol), s-phos (0.021 g, 0.05 mmol), potassium phosphate (0.441 g, 2.07 mmol) and toluene (5 mL). The flask is evacuated and filled with N2 thrice and Pd2(dba)3 (0.019 g, 0.02 mmol) is added. The flask is evacuated and filled with N2 thrice. The mixture is refluxed for 1 h, then cooled to room temperature and filtered through celite. The filtrate is concentrated in vacuo to afford 2-(5-chloro-pyridin-3-yl)-indole-1-carboxylic acid tert-butyl ester as an oil. The residue is dissolved in DCM (5 mL) and trifluoroacetic acid (2 mL) is added. The reaction mixture is stirred at room temperature for 4 h, followed with quenching with a saturated sodium bicarbonate solution. Extraction with dichloromethane, drying of the organic layer over sodium sulfate and concentration in vacuo gives a residue which is purified by silica gel flash chromatography (heptane-ethyl acetate, 3:2) to afford 2-(5-chloro-pyridin-3-yl)-1H-indole. 1H NMR (400 MHz, MeOD) δ ppm 7.06 (s, 1H), 7.08 (d, J=7.8 Hz, 1H), 7.20 (t, J=7.7 Hz, 1H), 7.45 (d, J=8.3 Hz, 1H), 7.61 (d, J=7.8 Hz, 1H), 8.30 (t, J=2.1 Hz, 1H), 8.47 (d, J=2.3 Hz, 1H), 8.96 (d, J=1.8 Hz, 2H). HRMS (ESI) m/z 229.0542 [(M+H)+ calcd for C13H10ClN2: 229.0533].

Aufarbeitung

  1. customThe flask is evacuated
  2. additionis added
  3. customThe flask is evacuated
  4. additionfilled with N2 thrice
  5. temperatureThe mixture is refluxed for 1 h
  6. filtrationfiltered through celite
  7. concentrationThe filtrate is concentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-6b101b9a76f34df1b1cbd36ab18aba58
Quelldatensatz
uspto-grants-2016_01
Patentnummer
US09242963B2

Notizen zur Reaktion

Wird geladen…