Isopropanol → 2'-[(t-Butoxycarbonylamino)methyl]-4-[(t-butyldiphenylsiloxy)methyl]-1,1'-biphenyl

HRID 1078154

Reaktionsgleichung

Reaktionsgleichung von HRID 1078154
[Si:1]([O:18][CH2:19][C:20]1[CH:25]=[CH:24][C:23](B(O)O)=[CH:22][CH:21]=1)([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH-].[Na+].C(O)(C)C.[C:35]([O:39][C:40]([NH:42][CH2:43][C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][C:45]=1Br)=[O:41])([CH3:38])([CH3:37])[CH3:36]>C1C=CC=CC=1.O.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:35]([O:39][C:40]([NH:42][CH2:43][C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][C:45]=1[C:23]1[CH:24]=[CH:25][C:20]([CH2:19][O:18][Si:1]([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[CH:21][CH:22]=1)=[O:41])([CH3:38])([CH3:36])[CH3:37]

Komponenten

8

Edukt 4

HCID 3776IsopropanolHCID 14798Sodium HydroxideHCID 70183002-Bromo-N-(tert-butoxycarbonyl)benzylamineHCID 15224568(4-(((tert-Butyldiphenylsilyl)oxy)methyl)phenyl)boronic acid

Produkt 1

HCID 220084542'-[(t-Butoxycarbonylamino)methyl]-4-[(t-butyldiphenylsiloxy)methyl]-1,1'-biphenylAusbeute 100 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumKatalysatorHCID 241BenzeneLösungsmittelHCID 962WaterLösungsmittel2×

Versuchsvorschrift

To a solution of 3.2 g (8.2 mmol) of 4-(t-butyldiphenylsilyoxymethyl)phenylboronic acid (Step B) in 64 mL of benzene was added 2.2 mL of water, 6.4 mL of 5N aqueous sodium hydroxide, and 8.3 mL of isopropanol. To this mixture was added 180 mg (0.16 mmol) of tetrakis(triphenylphosphine) palladium and 2.20 g (7.81 mmol) of N-(t-butoxycarbonyl)-2-bromobenzylamine (Step C). The resulting mixture was heated under nitrogen at reflux for 2 hours then cooled to room temperature. The reaction mixture was diluted with 100 mL of water, transferred to a separatory funnel and extracted with is ether (3×150 mL). The combined ether extracts were washed with saturated aqueous sodium bicarbonate (100 mL) and saturated aqueous sodium chloride (100 mL), dried over magnesium sulfate and filtered. The solvent was removed under vacuum to give a crude product which was purified by column chromatography on silica gel eluting with hexanes/ethyl acetate (9:1) to afford 4.31 g (100%) of the product as a clear oil. 1H NMR (200 MHz, CDCl3): δ1.11 (s, 9H), 1.41 (s, 9H), 4.27 (d, 6Hz, 2H), 4.45 (m, 1H), 4.81 (s, 2H), 7.20-7.49 (m, 14H), 8.72 (m, 4H). FAB-MS: calculated for C35H41NO3Si 551; found 552 (M+H).

Aufarbeitung

  1. temperatureThe resulting mixture was heated under nitrogen
  2. temperatureat reflux for 2 hours
  3. customtransferred to a separatory funnel
  4. extractionextracted
  5. washThe combined ether extracts were washed with saturated aqueous sodium bicarbonate (100 mL) and saturated aqueous sodium chloride (100 mL)
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. customThe solvent was removed under vacuum
  9. customto give a crude product which
  10. customwas purified by column chromatography on silica gel eluting with hexanes/ethyl acetate (9:1)

Quellen und Nachweise

ORD-Eintrag
ord-fb8d34f6f07f46ab8e151fe3d3d0071e
Quelldatensatz
uspto-grants-1996_08
Patentnummer
US05545735

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