Phenylboronic Acid → Ethyl 6-phenyl-3-(3-ethoxy-3-oxopropyl)-1H-indole-2-carboxylate

HRID 467430Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 467430
Br[C:2]1[CH:10]=[C:9]2[C:5]([C:6]([CH2:16][CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])=[C:7]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[NH:8]2)=[CH:4][CH:3]=1.[C:23]1(B(O)O)[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.O.O.O.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCOCC1>[C:23]1([C:2]2[CH:10]=[C:9]3[C:5]([C:6]([CH2:16][CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])=[C:7]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[NH:8]3)=[CH:4][CH:3]=2)[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Komponenten

6

Edukt 3

HCID 66827Phenylboronic AcidHCID 18407952Tripotassium phosphate trihydrateHCID 67315457ethyl 6-bromo-3-(3-ethoxy-3-oxopropyl)-1H-indole-2-carboxylate

Produkt 1

HCID 71281312Ethyl 6-phenyl-3-(3-ethoxy-3-oxopropyl)-1H-indole-2-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418476HCID 178418476, VerbindungKatalysatorHCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

Ethyl 6-bromo-3-(3-ethoxy-3-oxopropyl)-1H-indole-2-carboxylate (0.185 g, 0.500 mmol), phenylboronic acid (0.76 g, 0.625 mmol, 1.2 equiv.) and potassium phosphate trihydrate (0.200 g, 0.750 mmol, 1.5 equiv.) were mixed together in a 10 ml microwave vial. The vial was purged with Argon and trans-dichlorobis(triphenylphosphine)-palladium (II) (0.0105 g, 0.015 mmol, 3 mol %) and 5 ml of dry dioxane were added to the mixture. The microwave vial was capped and irradiated at 100 watt, 150° C., under pressure up to 10 bars. Then it was allowed to cool down to rt, and toluene was removed under reduced pressure and the residue was dissolved in dichloromethane and washed with water. The organic layer was dried over magnesium sulfate, filtered, and evaporated to dryness. The residue was purified by silica gel column chromatography using 20% of ethyl acetate/cyclohexane as eluent to yield a light-beige-colored solid in 70-80%. 1H-NMR (DMSO-d6) δ 1.11, 1.35 (each t, 3H, 3J=7.1 Hz, CH3); 2.60 (m, 2H, 2′-H); 3.31 (m, 2H, 1′-H); 3.99, 4.35 (each q, 2H, 4J=7.1 Hz, CH2); 7.35 (m, 2H, 4-H, 5-H); 7.46 (m, 2H, 2″-H, 6″-H); 7.62 (dd, 1H, 4″-H); 7.65 (m, 2H, 3″-H, 5″-H); 7.75 (dd, 1H, 7-H); 11.63 (s, 1H, NH). 13C-NMR (DMSO-d6) δ 14.9, 15.1 (2CH3, each C═OOCH2CH3); 20.90 (C-2′); 35.9 (C-1′); 60.7, 61.2 (2CH2, each C═OOCH2CH3); 111.0 (C-7); 120.1 (C-4); 121.8 (C-3); 122.3 (C-3a), 124.8 (C-5) 127.2 (C-2″, C-6″); 127.7 (C-4″); 128.0 (C-3″, C-5″); 129.8 (C-2); 137.7 (C-7a); 138.2 (C-6); 141.9 (C-1″); 162.3 (2′-CO2Et); 173.1 (2-CO2Et). LC-MS (m/z): 383 [M-NH4+]+, 366 [M]+, 364 [M]−. Purity LC-MS: 96%.

Aufarbeitung

  1. additionwere added to the mixture
  2. customThe microwave vial was capped
  3. customirradiated at 100 watt, 150° C., under pressure up to 10 bars
  4. customtoluene was removed under reduced pressure
  5. dissolutionthe residue was dissolved in dichloromethane
  6. washwashed with water
  7. dry with materialThe organic layer was dried over magnesium sulfate
  8. filtrationfiltered
  9. customevaporated to dryness
  10. customThe residue was purified by silica gel column chromatography
  11. customto yield a light-beige-colored solid in 70-80%

Quellen und Nachweise

ORD-Eintrag
ord-262ecaf6a0f64460929d33463e976c05
Quelldatensatz
uspto-grants-2014_01
Patentnummer
US08623593B1

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