Sodium Iodide → 4-trimethylsilanyloxy-7,8-dihydro-6H-cyclohepta[b]pyrrole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester

HRID 497392Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 497392
[CH2:1]([O:3][C:4]([C:6]1[C:7]2[C:22](=[O:23])[CH2:21][CH2:20][CH2:19][CH2:18][C:8]=2[N:9]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH:10]=1)=[O:5])[CH3:2].[Na+].[I-].C(N(CC)CC)C.[CH3:33][Si:34](Cl)([CH3:36])[CH3:35]>CC#N>[CH2:1]([O:3][C:4]([C:6]1[C:7]2[C:22]([O:23][Si:34]([CH3:36])([CH3:35])[CH3:33])=[CH:21][CH2:20][CH2:19][CH2:18][C:8]=2[N:9]([C:11]([O:13][C:14]([CH3:17])([CH3:15])[CH3:16])=[O:12])[CH:10]=1)=[O:5])[CH3:2]

Komponenten

6

Edukt 4

HCID 5238Sodium IodideHCID 6397ChlorotrimethylsilaneHCID 8471TriethylamineHCID 206056554-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[b]pyrrole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester

Produkt 1

HCID 207622254-trimethylsilanyloxy-7,8-dihydro-6H-cyclohepta[b]pyrrole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl esterAusbeute 100 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

To a solution of 4-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[b]pyrrole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester (2.17 g, 6.72 mmol), NaI (1.51 g, 10.07 mmol) and triethylamine (2.80 mL, 20.14 mmol) in CH3CN (30 mL), is added trimethylsilyl chloride (1.27 mL, 10.07 mmol) slowly via syringe. The reaction mixture is stirred at room temperature for 20 h. and then partitioned between 50 mL of ethyl acetate/hexanes (1:1 with a few drops of triethylamine) and 30 mL of sat. NaHCO3 solution. The layers are separated and the aqueous phase is extracted with ethyl acetate/hexanes (1:1) (3×20 mL). The combined organic layers are washed with brine, dried (Na2SO4) and evaporated to provide 4-trimethylsilanyloxy-7,8-dihydro-6H-cyclohepta[b]pyrrole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester (2.56 g, 100%) as viscous red oil. 1H NMR (400 MHz, CDCl3) δ 0.177 (9H, s), 1.308 (3H, t), 1.585 (9H, s), 1.906 (2H, m), 2.016 (2H, m), 2.974 (2H, t), 4.243 (2H, q), 5.353 (1H, t), 7.627 (1H, s). MS (ES+) 395 (M+1). Step 3:

Aufarbeitung

  1. custompartitioned between 50 mL of ethyl acetate/hexanes (1:1 with a few drops of triethylamine) and 30 mL of sat. NaHCO3 solution
  2. customThe layers are separated
  3. extractionthe aqueous phase is extracted with ethyl acetate/hexanes (1:1) (3×20 mL)
  4. washThe combined organic layers are washed with brine
  5. dry with materialdried (Na2SO4)
  6. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-5a821a45b40e4def8bdb0fd4682a406d
Quelldatensatz
uspto-grants-2005_09
Patentnummer
US06949562B2

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