Wacker Oxidation and Related Reactions

Handbook of Organopalladium Chemistry for Organic Synthesis, ed. E. Negishi, 2002. 

Note that the enolate is alkylated on the less-hindered face. 

FIGURE 23.27 Mechanism of hydrogenation using Wilkinson s catalyst. The sections in blue are not on the main catalytic pathway although they occur at measurable rates, these are at least 1000 

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J. Tsuji, Addition Reactions with Formation of Carbon-Oxygen Bonds - The Wacker Oxidation and Related Reactions, in Comprehensive Organic Synthesis (B. M. Trost, I. Fleming, Eds.), Vol. 7, 469, Pergamon Press, Oxford, U. K., 1991. 

Various oxidation reactions represented by Patterns 2 and 3 in Scheme 3 are discussed in Sect. VIII.3. However, the Wacker oxidation and related reactions, in which nucleophilic attack on Pd-alkene 7r-complexes plays an important role, are discussed in Sect. V.3. Most of the allylic substitution reactions represented by Pattern 4 are generally preceded by reduction of allylic electrophiles (via oxidative addition). Consequently, the overall processes do not generally involve net oxidation or reduction. So, they are discussed in Sect. V.II. 

J. Tsuji, Comp. Org. Synth, 1991, 7, 449-468. The Wacker Oxidation and Related Reactions. 

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