Tetrahydrofuran → (3S,7aR)-6,6-Dibenzyl-3-tert-butyl-1,6,7,7a-tetrahydro-5-oxopyrrolo[1,2-c]oxazole-7a-carboxylic Acid Methyl Ester

HRID 1359174

Reaktionsgleichung

Reaktionsgleichung von HRID 1359174
[CH3:1][O:2][C:3]([C@:5]12[CH2:16][CH2:15][C:14](=[O:17])[N:6]1[C@H:7]([C:10]([CH3:13])([CH3:12])[CH3:11])[O:8][CH2:9]2)=[O:4].[Li+].[CH3:19][CH:20]([N-]C(C)C)[CH3:21].CN(P(N(C)C)(N(C)C)=O)C.BrCCC[CH:41]([C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1)C1C=CC=CC=1.[CH2:54]1[CH2:58]O[CH2:56][CH2:55]1>>[CH3:1][O:2][C:3]([C@:5]12[CH2:16][C:15]([CH2:41][C:48]3[CH:49]=[CH:50][CH:51]=[CH:52][CH:53]=3)([CH2:56][C:55]3[CH:21]=[CH:20][CH:19]=[CH:58][CH:54]=3)[C:14](=[O:17])[N:6]1[C@H:7]([C:10]([CH3:13])([CH3:12])[CH3:11])[O:8][CH2:9]2)=[O:4]

Komponenten

6

Edukt 5

HCID 8028Tetrahydrofuran2×HCID 12679HexamethylphosphoramideHCID 2724682Lithium diisopropylamideHCID 11053798(3S,7aR)-3-tert-Butyl-1,6,7,7a-tetrahydro-5-oxopyrrolo[1,2-c]oxazole-7a-carboxylic Acid Methyl Ester2×HCID 122234581,1-Diphenyl-4-bromobutane

Produkt 1

HCID 11069859(3S,7aR)-6,6-Dibenzyl-3-tert-butyl-1,6,7,7a-tetrahydro-5-oxopyrrolo[1,2-c]oxazole-7a-carboxylic Acid Methyl Ester

Versuchsvorschrift

To a solution of bicycle 17 (260 mg, 1.08 mmol) in THF (7.0 mL) under nitrogen were added at −78° C. successively a solution of LDA (1.5 M, 1.0 mL) and HMPA (1.0 mL). After 1 h, 4-bromo-1,1-diphenylbutane (360 mg, 1.25 mmol) in THF (3.0 mL) was added. After 6 h at −78° C., the reaction mixture was quenched with saturated NH4Cl solution. The product was extracted into EtOAc, and the combined organic layers were washed with brine, dried (Na2SO4), and concentrated under reduced pressure. Separation by column chromatography (SiO2, hexane/EtOAc 30:1) afforded starting material 17 (140 mg, 54% recovery) and compound 14g (70 mg, 31%) besides traces of 14h (2 mg) and 14i (2 mg).

Aufarbeitung

  1. waitAfter 6 h at −78° C.
  2. customthe reaction mixture was quenched with saturated NH4Cl solution
  3. extractionThe product was extracted into EtOAc
  4. washthe combined organic layers were washed with brine
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated under reduced pressure
  7. customSeparation by column chromatography (SiO2, hexane/EtOAc 30:1)
  8. customafforded

Quellen und Nachweise

ORD-Eintrag
ord-d2c3645142db4131a886605b00405aeb
Quelldatensatz
uspto-grants-2003_07
Patentnummer
US06599940B2

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