Triphenylphosphine → Ethyl 2-(2-(((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)(tert-butoxycarbonyl)amino)ethoxy)-3-bromo-6-methyl-5-((methylsulfonyl)oxy)benzoate

HRID 577556Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 577556
[Br:1][C:2]1[C:3]([OH:19])=[C:4]([C:10]([CH3:18])=[C:11]([O:13][S:14]([CH3:17])(=[O:16])=[O:15])[CH:12]=1)[C:5]([O:7][CH2:8][CH3:9])=[O:6].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:39]([O:46][C:47]1[C:52]([CH2:53][N:54]([CH2:62][CH2:63]O)[C:55](=[O:61])[O:56][C:57]([CH3:60])([CH3:59])[CH3:58])=[C:51]([CH3:65])[CH:50]=[C:49]([CH3:66])[N:48]=1)[C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1.O>[CH2:39]([O:46][C:47]1[C:52]([CH2:53][N:54]([C:55]([O:56][C:57]([CH3:59])([CH3:58])[CH3:60])=[O:61])[CH2:62][CH2:63][O:19][C:3]2[C:2]([Br:1])=[CH:12][C:11]([O:13][S:14]([CH3:17])(=[O:15])=[O:16])=[C:10]([CH3:18])[C:4]=2[C:5]([O:7][CH2:8][CH3:9])=[O:6])=[C:51]([CH3:65])[CH:50]=[C:49]([CH3:66])[N:48]=1)[C:40]1[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=1

Komponenten

7

Edukt 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 86723695Tert-butyl ((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)(2-hydroxyethyl)carbamateHCID 86723782Ethyl 3-bromo-2-hydroxy-6-methyl-5-((methylsulfonyl)oxy)benzoate

Produkt 1

HCID 86723783Ethyl 2-(2-(((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)(tert-butoxycarbonyl)amino)ethoxy)-3-bromo-6-methyl-5-((methylsulfonyl)oxy)benzoateAusbeute 53,6 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

A solution of ethyl 3-bromo-2-hydroxy-6-methyl-5-((methylsulfonyl)oxy)benzoate (116d, 593 mg, 1.5 mmol), triphenylphosphine (0.50 g, 1.9 mmol), and tert-butyl ((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)(2-hydroxyethyl)carbamate (Cpd LL, 0.54 g, 1.5 mmol) in tetrahydrofuran (12 mL) was cooled to 0° C. then diisopropyl azodicarboxylate (0.40 mL, 1.9 mmol) was added drop wise. The reaction was slowly warmed to room temperature and stirred overnight. The reaction was diluted with water (15 mL) and extracted with ethyl acetate (2×15 mL). The combined organic layers were washed with brine (15 mL), dried over magnesium sulfate, concentrated under vacuum, and purified by column chromatography (20% EtOAc/Heptane) to give ethyl 2-(2-(((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)(tert-butoxycarbonyl)amino)ethoxy)-3-bromo-6-methyl-5-((methylsulfonyl)oxy)benzoate (116e, 0.58 g, 52% yield) as a white solid.

Aufarbeitung

  1. extractionextracted with ethyl acetate (2×15 mL)
  2. washThe combined organic layers were washed with brine (15 mL)
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated under vacuum
  5. custompurified by column chromatography (20% EtOAc/Heptane)

Quellen und Nachweise

ORD-Eintrag
ord-2d94c3680ab24c958277d8ccc03aa2ef
Quelldatensatz
uspto-grants-2015_05
Patentnummer
US09040515B2

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