Sodium Bicarbonate → tert-butyl (2S)-2-{[tert-butyl(dimethyl)silyl]oxy}-3-phenoxypropyl{[(2S)-6-(2,2-dimethyl-4-oxo-4H-1,3-benzodioxin-7-yl)-3,4-dihydro-2H-chromen-2-yl]methyl}carbamate

HRID 47693Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 47693
[Si:1]([O:8][C@H:9]([CH2:39][O:40][C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)[CH2:10][N:11]([CH2:19][C@@H:20]1[CH2:29][CH2:28][C:27]2[C:22](=[CH:23][CH:24]=[C:25](B3OC(C)(C)C(C)(C)O3)[CH:26]=2)[O:21]1)[C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].FC(F)(F)S(O[C:53]1[CH:54]=[CH:55][C:56]2[C:61](=[O:62])[O:60][C:59]([CH3:64])([CH3:63])[O:58][C:57]=2[CH:65]=1)(=O)=O.C(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1.C1C=CC([PH+]([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C1C=CC([PH+]([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C(Cl)Cl.Cl[Pd]Cl.[Fe]>[Si:1]([O:8][C@H:9]([CH2:39][O:40][C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)[CH2:10][N:11]([CH2:19][C@@H:20]1[CH2:29][CH2:28][C:27]2[C:22](=[CH:23][CH:24]=[C:25]([C:53]3[CH:54]=[CH:55][C:56]4[C:61](=[O:62])[O:60][C:59]([CH3:64])([CH3:63])[O:58][C:57]=4[CH:65]=3)[CH:26]=2)[O:21]1)[C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2]

Komponenten

6

Edukt 3

HCID 516892Sodium BicarbonateHCID 22351418HCID 22351418, VerbindungHCID 86587741tert-butyl (2S)-2-{[tert-butyl(dimethyl)silyl]oxy}-3-phenoxypropyl{[(2S)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-dihydro-2H-chromen-2-yl]methyl}carbamate

Produkt 1

HCID 86587740tert-butyl (2S)-2-{[tert-butyl(dimethyl)silyl]oxy}-3-phenoxypropyl{[(2S)-6-(2,2-dimethyl-4-oxo-4H-1,3-benzodioxin-7-yl)-3,4-dihydro-2H-chromen-2-yl]methyl}carbamateAusbeute 76 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 53485975CID 53485975KatalysatorHCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

To a degassed solution of tert-butyl (2S)-2-{[tert-butyl(dimethyl)silyl]oxy}-3-phenoxypropyl{[(2S)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-dihydro-2H-chromen-2-yl]methyl}carbamate (1.0 g, 1.53 mmol, 1.0 eq.) in toluene (12 mL) were added 2,2-dimethyl-4-oxo-4H-1,3-benzodioxin-7-yl trifluoromethanesulfonate (0.60 g, 1.84 mmol, 1.2 equiv.), dichloro[1,1′-bis(diphenylphosphino)ferrocene] palladium(II) dichloromethane adduct (0.18 g, 0.23 mmol, 0.15 eq.) and saturated sodium bicarbonate (8.0 mL) under argon atmosphere at room temperature. The reaction mixture was allowed to heat up at 80° C. under argon atmosphere for 18 hours. The mixture was then quenched with distilled water (10 mL) and extracted with ethyl acetate (3×10 mL). The combined extracts were washed with brine (20 mL), dried over magnesium sulfate, filtered and concentrated under reduced pressure to afford black oil. Purification by flash chromatography on a silica gel column (5%-15% ethyl acetate/hexanes) yielded the desired product as colorless oil (0.81 g, 76%). 1H NMR (CDCl3) δ7.86 (d, 1 H), 7.27-6.78 (m, 11H), 4.20-3.85 (m, 2H), 3.81-3.40 (m, 4H), 3.37-3.20 (m, 2H), 2.80-2.21 (m, 2H), 1.95-1.84 (m, 1H), 1.64 (s, 7H), 1.39 (s, 9H), 0.81 (s, 9H), 0.020 (s, 6H).

Aufarbeitung

  1. customThe mixture was then quenched with distilled water (10 mL)
  2. extractionextracted with ethyl acetate (3×10 mL)
  3. washThe combined extracts were washed with brine (20 mL)
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customto afford black oil
  8. customPurification by flash chromatography on a silica gel column (5%-15% ethyl acetate/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-687b92fbaa4944b9bdbcd8445fb7d6da
Quelldatensatz
uspto-grants-2004_03
Patentnummer
US06699860B2

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