Slappy (Moderator)
08-31-99 04:37
No 103613
      Oxidation of terminal olefins with Tetrakis(Triphenylphosphine)Palladium(0)
(Rated as: good read)

Oxidation of terminal olefins with Tetrakis(Triphenylphosphine)Palladium(0)

Gazz Chim Ital 122, 531-532 (1992) (English)

Solvent: 3.2M aqueous H2O2 solution.
Reaction conditions: 72h stirring at ~50C.
Catalysis statistics: 2000:1 molar ratio alkene:catalyst
Conversion & Selectivity: 99%+

Terminal Olefins can be oxidised under mild conditions in exellent yields and selectivities to methyl ketones by employing an auqeous medium containing hydrogen peroxide as the oxidant and tetrakis(triphenylphosphine)palladium(0) as the catalyst.

Palladium(0)-catalysed oxidation of terminal alkenes with Hydrogen Peroxide in a heterogeneous aqueous medium.

Olefin / Product / Conversion / Selectivity / Reaction Temp.
1-hexene / 2-hexanone / >99% / >99% / 40C
1-heptene / 2-heptanone / >99% / >99% / 50C
1-octene / 2-octanone / 98% / >99% / 50C
1-decene / 2-decanone / 98% / >99% / 80C
1-octadecene / 2-octadecanone / 10% >99% / 80C

Rhodium posted this in the Serious Chemistry Forum a while back. Has anyone else taken a look at this? If this will work with Safrole, and I see no reason why it wouldn't, we would have the perfect method. Minimal equipment, easy procedure, no isomerized alkene, it seems perfect to me.

In case you were wondering, Tetrakis(Triphenylphosphine)Palladium(0) is used in industry, and is available from all the major chem companies (Alfa, TCI, Etc.) for a fair price, about the same or cheaper than PdCl2. Plus, you are using only a fraction of the amount (5g for 100g olefin as opossed to 500mg for 100g olefin). And it is totally unwatched.

Any thoughts/comments? I am going to try and give it a runs as soon as I can get my hands on the catalyst.

08-31-99 15:39
No 103614
      Re: Oxidation of terminal olefins with Pd(PPh3)4     

I spoke with someone who tried the method, but didn't give much details. His only tip was to run the reaction at 25-30C until TLC (hexane/ethyl acetate 4:1) showed that the starting material was consumed, then do the workup. Too high rxn temps apparently messed things up.
(Chief Bee)
03-19-04 08:28
No 496153
      Super clean wacker variation     

This reaction deserves a *bump* to the forum top. Anyone have the full article in PDF?

The Hive - Clandestine Chemists Without Borders
03-23-04 17:56
No 496943
      Ioele's paper
(Rated as: good read)

Ioele et al's paper in Deja Vu format:

Gazz Chim Ital 122, 531-532 (1992)


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