Computational Insights into Palladium-Mediated Allylic Substitution Reactions

Allyl palladium complexes have a rich chemistry. Many aspects of their structure and reactivity have been studied computationally. This chapter gives an overview of the history in this field, from structural studies and the effect of ligands and substituents, to the rich reactivity of the title complexes. The latter includes complex formation, reactions with nucleophiles and electrophiles, and dynamic equilibria. An important focus area has been the Tsuji-Trost reaction, in particular asymmetric versions thereof. A brief overview of computational methods, aimed at modeling novices, can be found in the introduction.