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. 2005 Mar 9;127(9):2796-7.
doi: 10.1021/ja043203m.

Discovery of and mechanistic insight into a ligand-modulated palladium-catalyzed Wacker oxidation of styrenes using TBHP

Candace N Cornell  1 , Matthew S Sigman
Affiliations

Discovery of and mechanistic insight into a ligand-modulated palladium-catalyzed Wacker oxidation of styrenes using TBHP

Candace N Cornell et al. J Am Chem Soc. .

Abstract

We describe the discovery of a new N-heterocyclic carbene-modulated Pd catalyst for the Wacker oxidation that does not require molecular oxygen but instead uses TBHP as a reagent in this oxidation. The catalyst activity and selectivity for the oxidation of styrene derivatives to methyl ketones are among the best reported. Preliminary mechanistic studies of the catalytic system were performed and show that the origin of the carbonyl oxygen is TBHP and that the hydrogens in the product all originate from the starting olefin.

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Figures

Figure 1
Figure 1
In situ FTIR monitoring the disappearance of styrene via C–H out of plane deformation at 702.9 cm−1 and formation of γ-butyrolactone via the CO stretch at 1779.5 cm−1.
Figure 2
Figure 2
X-ray crystal structure of Pd(IiPr)(OH2)3•(OTf)2•(H2O)2. Two OTf counterions and two H2O molecules are excluded for clarity.
Scheme 1
Scheme 1
Commonly Proposed Mechanistic Pathways for Olefin Oxidation
See this image and copyright information in PMC

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