6-Bromopyridine-2-carbaldehyde → tert-Butyl {[1-(6-formylpyridin-2-yl)-2-naphthyl]methyl}phenylcarbamate

HRID 2370666Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2370666
Br[C:2]1[N:7]=[C:6]([CH:8]=[O:9])[CH:5]=[CH:4][CH:3]=1.[C:10]1([N:16]([CH2:24][C:25]2[CH:34]=[CH:33][C:32]3[C:27](=[CH:28][CH:29]=[CH:30][CH:31]=3)[C:26]=2B2OC(C)(C)C(C)(C)O2)[C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:21])[CH3:20])[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1>CO.O.C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH:8]([C:6]1[N:7]=[C:2]([C:26]2[C:27]3[C:32](=[CH:31][CH:30]=[CH:29][CH:28]=3)[CH:33]=[CH:34][C:25]=2[CH2:24][N:16]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:20])[CH3:21])[CH:3]=[CH:4][CH:5]=1)=[O:9]

Komponenten

7

Edukt 2

HCID 27570096-Bromopyridine-2-carbaldehydeHCID 66796055tert-Butyl phenyl{[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-naphthyl]methyl}carbamate

Produkt 1

HCID 86660102tert-Butyl {[1-(6-formylpyridin-2-yl)-2-naphthyl]methyl}phenylcarbamate

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 887MethanolLösungsmittelHCID 962WaterLösungsmittelHCID 1140TolueneLösungsmittel

Versuchsvorschrift

A solution of 24.3 g (84.8 mmol) of Na2CO3(H2O)10 in a mixture of 120 ml of methanol and 450 ml of water was added to a mixture of 6.30 g (33.9 mmol) of 6-bromopyridine-2-carbaldehyde, 15.6 g (33.9 mmol) of tert-butyl phenyl{[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-naphthyl]methyl}carbamate and 1.96 g (1.70 mmol) of Pd(PPh3)4 in 600 ml of toluene by vigorous stirring at room temperature. The resulting mixture was stirred at 80° C. for 12 h. Thereafter, this mixture was cooled to room temperature, the organic layer was separated, dried over MgSO4, and then evaporated to dryness. The product was isolated by flash chromatography on silica gel 60 (40-63 um; eluent: hexanes-ethyl acetate=50:1 and then 10:1, vol.). Yield 9.50 g (64%). Anal. calc. for C28H26N2O3: C, 76.69; H, 5.98; N, 6.39. Found: C, 76.87; H, 6.12; N, 6.25. 1H NMR (CDCl3): 10.03 (s, 1H, CHO), 7.94-7.98 (m, 2H, 3,5-H in Py), 7.88 (m, 1H, 8-H in naphthyl), 7.83 (m, 1H, 4-H in Py), 7.75 (d, J=8.6 Hz, 1H, 4-H in naphthyl), 7.45 (m, 1H, 7-H in naphthyl), 7.34 (m, 1H, 6-H in naphthyl), 7.11-7.18 (m, 4H, 5-H in naphthyl and 3,4,5-H in Ph), 7.03 (d, J=8.6 Hz, 1H, 3-H in naphthyl), 6.93 (m, 2H, 2,6-H in Ph), 5.06 (d, J=15.9 Hz, 1H, CHH′N), 4.52 (d, J=15.9 Hz, 1H, CHH′N), 1.40 (s, 9H, tBu).

Aufarbeitung

  1. stirringThe resulting mixture was stirred at 80° C. for 12 h
  2. temperatureThereafter, this mixture was cooled to room temperature
  3. customthe organic layer was separated
  4. dry with materialdried over MgSO4
  5. customevaporated to dryness
  6. customThe product was isolated by flash chromatography on silica gel 60 (40-63 um

Quellen und Nachweise

ORD-Eintrag
ord-9a485591168644ca9d8b9197eea8149e
Quelldatensatz
uspto-grants-2014_04
Patentnummer
US08710163B2

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