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Ammonium Hydroxide → (R)-tert-butyl 2-(2,5-difluorophenyl)pyrrolidine-1-carboxylate

HRID 1893759
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1893759
[C:1]([O:5][C:6]([N:8]1[CH2:12][CH2:11][CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C1C[C@H]2N(C[C@H]3[C@@H]4CCCCN4C[C@@H]2C3)CC1.[Li]C(CC)C.Br[C:36]1[CH:41]=[C:40]([F:42])[CH:39]=[CH:38][C:37]=1[F:43].[NH4+].[OH-]>CC(OC)(C)C.[Cl-].[Cl-].[Zn+2].CC([O-])=O.CC([O-])=O.[Pd+2].P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.[H+].[B-](F)(F)(F)F>[F:42][C:40]1[CH:41]=[CH:36][C:37]([F:43])=[CH:38][C:39]=1[C@H:9]1[CH2:10][CH2:11][CH2:12][N:8]1[C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:7]
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

10

Edukt 5

HCID 14923Ammonium HydroxideHCID 678622-Bromo-1,4-difluorobenzeneHCID 643455N-Boc-pyrrolidineHCID 644020SparteineHCID 178418400CID 53628100

Produkt 1

HCID 66847700(R)-tert-butyl 2-(2,5-difluorophenyl)pyrrolidine-1-carboxylateAusbeute 72,2 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 167845palladium(II) acetateKatalysatorHCID 3007855ZincchlorideKatalysatorHCID 118705180Tris(tert-butyl)phosphonium tetrafluoroborateKatalysatorHCID 15413tert-Butyl methyl etherLösungsmittel

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

A solution of tert-butylpyrrolidine-1-carboxylate (20 g, 116.8 mmol) and (−)sparteine (32.9, 140 mmol) in MTBE (360 mL) was cooled to −78° C., and sec-BuLi (100 mL, 140 mmol, 1.4 M in cyclohexane) was introduced dropwise via cannula, keeping the internal temperature under −70° C. The resulting solution was stirred for 3 hours at −78° C., followed by addition of a solution of ZnCl2 (93.4 mL, 93.4 mmol, 1M in Et2O) drop-wise with rapid stirring, keeping the internal temperature below −65° C. The resulting light suspension was stirred at −78° C. for 30 minutes and then warmed to ambient temperature. The resulting mixture was charged with 2-bromo-1,4-difluorobenzene (14.5 mL, 128 mmol), followed by Pd(OAc)2 (1.31 g, 5.8 mmol) and t-Bu3P—HBF4 (2.03 g, 7.0 mmol) in one portion. After stirring overnight at ambient temperature, 10.5 mL of NH4OH solution was added and the reaction was stirred for another hour. The resulting slurry was filtered through CELITE and washed with Et2O (1 L). The filtrate was washed with HCl (0.5 L, 1M aq.) and brine. The organic layer was filtered and concentrated, and the crude product was purified by silica column chromatography, eluting with 5-10% EtOAc/hexanes to give product (R)-tert-butyl 2-(2,5-difluorophenyl)pyrrolidine-1-carboxylate as yellow oil (23.9 g, 72% yield).

Aufarbeitung

  1. customunder −70° C
  2. customthe internal temperature below −65° C
  3. stirringThe resulting light suspension was stirred at −78° C. for 30 minutes
  4. temperaturewarmed to ambient temperature
  5. stirringAfter stirring overnight at ambient temperature
  6. stirringthe reaction was stirred for another hour
  7. filtrationThe resulting slurry was filtered through CELITE
  8. washwashed with Et2O (1 L)
  9. washThe filtrate was washed with HCl (0.5 L, 1M aq.) and brine
  10. filtrationThe organic layer was filtered
  11. concentrationconcentrated
  12. customthe crude product was purified by silica column chromatography
  13. washeluting with 5-10% EtOAc/hexanes

Quellen und Nachweise

ORD-Eintrag
ord-fa54d99b7a4e443e9870308e49a3c873
Quelldatensatz
uspto-grants-2013_08
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08513263B2

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