Ethyl Acetate → (S,E)-(2-((tert-butyldimethylsilyloxy)methyl)-4-(prop-1-enyl)-2,3-dihydro-1H-pyrrol-1-yl)(5-methoxy-2-nitro-4-(triisopropylsilyloxy)phenyl)methanone

HRID 513357

Reaktionsgleichung

Reaktionsgleichung von HRID 513357
FC(F)(F)S(O[C:7]1[CH2:11][C@@H:10]([CH2:12][O:13][Si:14]([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15])[N:9]([C:21](=[O:44])[C:22]2[CH:27]=[C:26]([O:28][CH3:29])[C:25]([O:30][Si:31]([CH:38]([CH3:40])[CH3:39])([CH:35]([CH3:37])[CH3:36])[CH:32]([CH3:34])[CH3:33])=[CH:24][C:23]=2[N+:41]([O-:43])=[O:42])[CH:8]=1)(=O)=O.[CH:47](/B(O)O)=[CH:48]\[CH3:49].P([O-])([O-])([O-])=O.[K+].[K+].[K+].C(OCC)(=O)C>O1CCOCC1.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.O>[Si:14]([O:13][CH2:12][C@@H:10]1[CH2:11][C:7](/[CH:47]=[CH:48]/[CH3:49])=[CH:8][N:9]1[C:21]([C:22]1[CH:27]=[C:26]([O:28][CH3:29])[C:25]([O:30][Si:31]([CH:32]([CH3:34])[CH3:33])([CH:38]([CH3:39])[CH3:40])[CH:35]([CH3:36])[CH3:37])=[CH:24][C:23]=1[N+:41]([O-:43])=[O:42])=[O:44])([C:17]([CH3:18])([CH3:19])[CH3:20])([CH3:16])[CH3:15]

Komponenten

8

Edukt 4

HCID 8857Ethyl AcetateHCID 62657Potassium Phosphate, TribasicHCID 6157276((1E)-prop-1-en-1-yl)boronic acidHCID 71550534(S)-5-((tert-butyldimethylsilyloxy)methyl)-1-(5-methoxy-2-nitro-4-(triisopropylsilyloxy)benzoyl)-4,5-dihydro-1H-pyrrol-3-yl trifluoromethanesulfonate

Produkt 1

HCID 86717761(S,E)-(2-((tert-butyldimethylsilyloxy)methyl)-4-(prop-1-enyl)-2,3-dihydro-1H-pyrrol-1-yl)(5-methoxy-2-nitro-4-(triisopropylsilyloxy)phenyl)methanoneAusbeute 70 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
25 °C

Versuchsvorschrift

Tetrakis(triphenylphosphine)palladium(0) (0.41 g, 0.35 mmol, 0.03 eq) was added to a mixture of the triflate 5 (8.4 g, 11.8 mmol, 1.0 eq), E-1-propene-1-ylboronic acid (1.42 g, 16.5 mmol, 1.4 eq) and potassium phosphate (5.0 g, 23.6 mmol, 2.0 eq) in dry dioxane (60 mL) under a nitrogen atmosphere. The mixture was stirred at 25° C. for 120 mins when LC/MS indicated complete reaction. Ethyl acetate (120 mL) and water (120 mL) were added, the organic phase was removed, washed with brine (20 mL), dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (silica gel, 95/5 v/v n-hexane/EtOAc to 90/10 v/v n-hexane/EtOAc) to afford the product as a yellow foam (4.96 g, 70%). LC/MS (4.477 min (ES+)), m/z: 605.0 [M+H]+. 1H NMR (400 MHz, CDCl3) δ 7.67 (s, 1H), 6.74 (s, 1H), 5.93 (d, 1H, J=15.4 Hz), 5.67 (s, 1H), 4.65 (m, 1H), 4.04 (m, 2H), 3.86 (s, 3H), 2.85 (m, 1H), 2.71 (m, 1H), 1.72 (dd, 3H, J=6.8, 1.0 Hz), 1.30-1.22 (m, 3H), 1.07 (d, 18H, J=7.2 Hz), 0.87 (s, 9H), 0.08 (s, 3H), 0.07 (s, 3H).

Aufarbeitung

  1. customreaction
  2. customthe organic phase was removed
  3. washwashed with brine (20 mL)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by flash chromatography (silica gel, 95/5 v/v n-hexane/EtOAc to 90/10 v/v n-hexane/EtOAc)

Quellen und Nachweise

ORD-Eintrag
ord-cfcd74d726c74eb38d09f8c8a8256876
Quelldatensatz
uspto-grants-2015_08
Patentnummer
US09102704B2

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