2,7-Dibromo-9-fluorenone → 2-[N-Boc-3,7-diazabicyclo[3.3.0]octan-3-yl]-7-bromofluoren-9-one

HRID 902970Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 902970
[C:1]([N:8]1[CH2:15][CH:14]2[CH:10]([CH2:11][NH:12][CH2:13]2)[CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[Br:16][C:17]1[CH:29]=[CH:28][C:27]2[C:26]3[C:21](=[CH:22][C:23](Br)=[CH:24][CH:25]=3)[C:20](=[O:31])[C:19]=2[CH:18]=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:1]([N:8]1[CH2:9][CH:10]2[CH:14]([CH2:13][N:12]([C:23]3[CH:24]=[CH:25][C:26]4[C:27]5[C:19](=[CH:18][C:17]([Br:16])=[CH:29][CH:28]=5)[C:20](=[O:31])[C:21]=4[CH:22]=3)[CH2:11]2)[CH2:15]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2]

Komponenten

7

Edukt 3

HCID 2599222,7-Dibromo-9-fluorenoneHCID 4142526Tert-butyl octahydropyrrolo(3,4-c)pyrrole-2-carboxylateHCID 23676156Sodium t-butoxide

Produkt 1

HCID 671640772-[N-Boc-3,7-diazabicyclo[3.3.0]octan-3-yl]-7-bromofluoren-9-oneAusbeute 75,5 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 634876Binap, (A+-)-KatalysatorHCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
85 °C

Versuchsvorschrift

A mixture of 3-Boc-3,7-diazabicyclo[3.3.0]octane (2.12 g, 10.0 mmol; see WO 0181347), 2,7-dibromofluoren-9-one (6.76 g, 20.0 mmol; Aldrich), tris(dibenzylideneacetone)dipalladium(0) (Pd2dba3; 185 mg, 0.202 mmol; Strem), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP; 310 mg, 0.498 mmol; Strem) and sodium tert-butoxide (1.4 g, 14.6 mmol; Aldrich) in 100 mL toluene was warmed to 85° C. and stirred for 9 h. The reaction mixture was cooled to ambient temperature and filtered through diatomaceous earth, rinsing with dichloromethane. After concentrating the solution under reduced pressure, the residue was purified by column chromatography (silica gel, 10-60% EtOAc/hexanes) to give the title compound (3.54 g, 7.55 mmol, 75% yield). MS (DCl/NH3): m/z 469, 471 (M+1)+.

Aufarbeitung

  1. temperatureThe reaction mixture was cooled to ambient temperature
  2. filtrationfiltered through diatomaceous earth
  3. washrinsing with dichloromethane
  4. concentrationAfter concentrating the solution under reduced pressure
  5. customthe residue was purified by column chromatography (silica gel, 10-60% EtOAc/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-ab3016826f5d4289b43a3160ad331e02
Quelldatensatz
uspto-grants-2008_04
Patentnummer
US07365193B2

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