Steric Influences on the Selectivity in Palladium-Catalyzed Allylation

The product distribution from nucleophilic attack on (η 3 -allyl)palladium complexes is analyzed by a combination of molecular mechanics and QSAR techniques. A predictive model has been derived from a training set carefully chosen to minimize effects from solvent, nucleophile, and electronic influences in allyl and ligand. The model shows good cross-validated predictive power and has been used to evaluate the relative importance of different steric influences on regio- and stereoselectivity in the title reaction.