Tetrafluoroboric acid → Hedione

HRID 1281652

Reaktionsgleichung

Reaktionsgleichung von HRID 1281652
C[C@H]1P(C2C(P3[C@H](C)CC[C@H]3C)=CC=CC=2)[C@H](C)CC1.[O:21]=[C:22]1[CH2:26][CH2:25][C:24]([CH2:27][C:28]([O:30][CH3:31])=[O:29])=[C:23]1[CH2:32][CH2:33][CH2:34][CH2:35][CH3:36].[H+].[B-](F)(F)(F)F>C(Cl)Cl>[CH3:36][CH2:35][CH2:34][CH2:33][CH2:32][CH:23]1[C:22](=[O:21])[CH2:26][CH2:25][CH:24]1[CH2:27][C:28]([O:30][CH3:31])=[O:29]

Komponenten

5

Edukt 3

HCID 28118Tetrafluoroboric acidHCID 906341-Cyclopentene-1-acetic acid, 3-oxo-2-pentyl-, methyl ester2×HCID 2734551Methyl-duphos, (R,R)-

Produkt 1

HCID 102861HedioneAusbeute 99 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

In a glovebox, into a 10 ml glass vial were placed 15.5 mg (0.0485 mmole) of [(COD)Ru(2-methylallyl)2], 14.9 mg (0.0485 mmole) of (R,R)-Me-DuPHOS and 250 μl of methyl 3-oxo-2-pentyl-1-cyclopentene-1-acetate (1.08 nmuole). To this suspension was added 0.630 ml of a 0.081 M solution of titrated HBF4.etherate (0.049 nunole) in CH2Cl2 with stirring. This concentrated solution was stirred for 1.5 hours, after which 21.5 g (95.9 mmole) of methyl 3-oxo-2-pentyl-1-cyclopentene-1-acetate and 11.5 ml of CH2Cl2 were added. The resulting yellow solution was placed in a 75 ml autoclave, purged with hydrogen and pressurized to 90 bar of hydrogen. After 8 hours, the solution was exposed to air and passed through a column of silica gel to separate the catalyst. This gave a 99% yield of the desired Hedione® product with the following ratios of isomers: cis/trans=98/2; (+)-cis/(−)-cis=82.4/17.6, 64.8% ee.

Aufarbeitung

  1. custompurged with hydrogen
  2. waitAfter 8 hours
  3. customto separate the catalyst

Quellen und Nachweise

ORD-Eintrag
ord-02bc642964574cf48e5b21e49f050856
Quelldatensatz
uspto-grants-2002_09
Patentnummer
US06455460B1

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