Charge-affinity inverted reactions

Curiously, both of the prototypical reactions shown in Scheme 1 involve the use of allyl- or benzyhnetals. Their charge affinity-inverted versions, which are currently much more commonly employed, were reported by Tamao et al. in 1978 on aUylation and by Milstein and Stille in 1979 on benzylation (Scheme 2). Thus, the foundation of Pd-catalyzed aUylation and benzylation was laid in the late 1970s. Of Pd-catalyzed aUylation, benzylation, and propargylation, aUylation has been most extensively investigated by far. 

In this section, attention is focused on the Pd-catalyzed a-substitution reactions of enolates and related derivatives represented by Method I in Scheme 1, other than Tsuji-Trost allylation and propargylation. Additionally, its charge-affinity inverted version represented by Method II in Scheme 1 is also discussed. In general, it is advisable to consider simultaneously various other alternatives including those shown in Scheme 1, especially Method III. Indeed, Method III discussed in the following section provides the currently most... 

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