HCID 86675581, Verbindung → HCID 71183845, Verbindung

HRID 1422598Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1422598
[N+](=[C:3]([C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([N+:16]([O-:18])=[O:17])[CH:11]=1)[C:4]([O:6][CH2:7][CH:8]=[CH2:9])=[O:5])=[N-]>ClCCl.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.[Rh+2].[Rh+2]>[N+:16]([C:12]1[CH:11]=[C:10]([C:3]23[CH2:9][CH:8]2[CH2:7][O:6][C:4]3=[O:5])[CH:15]=[CH:14][CH:13]=1)([O-:18])=[O:17]

Komponenten

4

Edukt 1

HCID 86675581HCID 86675581, Verbindung

Produkt 1

HCID 71183845HCID 71183845, VerbindungAusbeute 91,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 11621934Rhodium(II) octanoate dimerKatalysatorHCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

To a solution of commercially available rhodium(II) octanoate dimer (Rh2(C7H16CO2)4) CAS-no. [73482-96-9] (440 mg, 565 μmol, Eq: 0.00941) in dichloromethane (180 ml) at 50° C. was added a solution of allyl 2-diazo-2-(3-nitrophenyl)acetate (intermediate B4a) (14.85 g, 60.1 mmol, Eq: 1.00) in dichloromethane (38 ml) via syringe pump within 18 h. Refluxing was continued for 30 min, the solvent was evaporated and the crude material was purified by flash chromatography (silica gel, 70 g, 0% to 100% EtOAc in heptane) to give (1SR,5RS)-1-(3-nitrophenyl)-3-oxabicyclo[3.1.0]hexan-2-one (12 g, 54.7 mmol, 91.1% yield) as a light brown solid. [cf. Adv. Synth. Catal. 2001, 343, 299 for an enantioselective version of this reaction]. MS (ISP): m/z=237.1 [(M+NH4)+].

Aufarbeitung

  1. temperatureRefluxing
  2. customthe solvent was evaporated
  3. customthe crude material was purified by flash chromatography (silica gel, 70 g, 0% to 100% EtOAc in heptane)

Quellen und Nachweise

ORD-Eintrag
ord-1e705b2ec02c4285bdc0f39540511412
Quelldatensatz
uspto-grants-2015_01
Patentnummer
US08927535B2

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