Triphenylphosphine → HCID 86596146, Verbindung

HRID 2222929Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2222929
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O.O[CH2:35][CH:36]1[CH2:41][CH2:40][CH:39]([CH3:42])[CH2:38][CH:37]1[C:43]([O:45][CH2:46][CH3:47])=[O:44].[F:48][C:49]1[CH:54]=[CH:53][C:52]([SH:55])=[CH:51][CH:50]=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C)C=O.[Cl-].[Na+].O.CCOCC>[F:48][C:49]1[CH:54]=[CH:53][C:52]([S:55][CH2:35][CH:36]2[CH2:41][CH2:40][CH:39]([CH3:42])[CH2:38][CH:37]2[C:43]([O:45][CH2:46][CH3:47])=[O:44])=[CH:51][CH:50]=1

Komponenten

9

Edukt 5

HCID 11776TriphenylphosphineHCID 677894-FluorothiophenolHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 86593035HCID 86593035, VerbindungHCID 86596147HCID 86596147, Verbindung

Produkt 1

HCID 86596146HCID 86596146, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 3283Diethyl EtherLösungsmittelHCID 6228DimethylformamideLösungsmittel2×HCID 57417360Sodium chloride; waterLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a cold (0° C.) solution of triphenylphosphine (260 mg, 1.0 mmol) in dimethylformamide (1 mL) was added diisopropyl azodicarboxylate (180 μL, 0.9 mmol) and the reaction mixture was stirred at 0° C. for 10 min. A mixture of (1R/S,3R/S,6R/S)-ethyl 2-(hydroxymethyl)-5-methylcyclohexanecarboxylate and (1R/S,3S/R,6R/S)-ethyl 2-(hydroxymethyl)-5-methylcyclohexanecarboxylate (1:1 mixture, 160 mg, 0.8 mmol) and 4-fluorobenzenethiol (100 μL, 0.9 mmol) in dimethylformamide (1 mL) was added to the diisopropyl azodicarboxylate/triphenylphosphine mixture. The reaction mixture was warmed to room temperature and stirred for 3 h. Ether and brine were added and the aqueous layer was extracted with ether. The combined organic extracts were concentrated in vacuo and the residue was purified by flash chromatography over silica gel (ether/hexanes, 5/95) to afford the product (1R/S,3R/S,6R/S)-ethyl 2-{[(4-fluorophenyl)sulfanyl]methyl}-5-methylcyclohexanecarboxylate and (1R/S,3S/R,6R/S)-ethyl 2-{[(4-fluorophenyl)sulfanyl]methyl}-5-methylcyclohexane-carboxylate as a 1:1 mixture of diastereomers.

Aufarbeitung

  1. temperatureThe reaction mixture was warmed to room temperature
  2. stirringstirred for 3 h
  3. extractionthe aqueous layer was extracted with ether
  4. concentrationThe combined organic extracts were concentrated in vacuo
  5. customthe residue was purified by flash chromatography over silica gel (ether/hexanes, 5/95)

Quellen und Nachweise

ORD-Eintrag
ord-5847444b7fc841cea31a77b0c481b000
Quelldatensatz
uspto-grants-2008_05
Patentnummer
US07371747B2

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