Wacker Oxidation of Alkenes Explained
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MANIKANDAN MWacker Oxidation of Alkenes Explained
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MANIKANDAN MWACKER PROCESS
PRESENTED BY
MANIKANDAN M
II MSc Chemistry
SRMV CAS
COIMBATORE
WACKER PROCESS
The Wacker oxidation refers generally to the transformation of a terminal or 1,2-disubstituted alkene to a
ketone through the action of catalytic palladium(II), water, and a co-oxidant. Variants of the reaction yield
aldehydes, vinylic ethers, and vinylic amines.
The stoichiometric conversion of ethylene to acetaldehyde by an acidic, aqueous solution of PdCl2 was
discovered over a century ago, but fifty years passed between the discovery of this reaction and the
development of a catalytic method. In 1959, researchers at Wacker Chemie reported that a similar
transformation takes place in an aqueous, acidic solution of catalytic PdCl2 and a stoichiometric amount of
CuCl2 through which oxygen is bubbled.
To encourage mixing of the organic reactants with the aqueous phase, a co-solvent is generally employed
along with water. Dimethylformamide (DMF) is a common choice; when DMF is used as a co-solvent
with a stoichiometric amount of CuCl under balloon pressure of oxygen, the reaction is called the “Tsuji-
Wacker oxidation”.
MECHANISM
rate-limiting step
β-hydride elimination
SCOPE AND LIMITATIONS
General Functional-Group Tolerance
Oxygen-Containing Functional Groups
Substrates bearing oxygen containing functional groups are well-tolerated, except when they are in close
proximity to the reacting double bond.
Carbonyl compounds such as ketones, carboxylic acids, and esters are also compatible functional groups,
including instances of β-dicarbonyls bearing an acidic α-proton. It is also worth noting that only the terminal
alkene is oxidized in this diene substrate, which is the outcome typically observed.
Under Tsuji–Wacker type conditions alcohols are not oxidized, despite relatively similar conditions to Pd-
catalyzed alcohol oxidations. This result is indicative of the preference for palladium to interact with the π-
bond of an alkene, as compared to the lone pair of an alcohol (a common solvent for Wacker oxidations).
This phenomenon can be further highlighted in the selective reaction of the alkene even in highly
oxygenated substrates, which do not require extended reaction times or high catalyst loadings
Substrates with Multiple Alkenes
The reaction of multiple terminal alkenes in the same substrate has been demonstrated using Tsuji–Wacker
oxidation conditions.
The presence of two differentially substituted alkenes in the same substrate raises a number of interesting
considerations, although terminal alkenes generally react faster than internal alkenes as illustrated below
where the substrate contains both an internal cis-disubstituted alkene and a terminal alkene.
The 1,4-diene is selectively oxidized in methanol at the terminal alkene in preference to the internal
styrenyl alkene. This reaction presumably provides the dimethyl acetal initially, which is readily converted
into the methyl ketone upon workup with 10% HCl solution.
REFERENCE
THE WACKER OXIDATION
Brian W. Michel, Laura D. Steffens, and Matthew S.
Sigman
THANK
Department of Chemistry, University of Utah, 315 S 1400 E,
Salt Lake City,
UT 84112-0850
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