Tsuji-Trost Allylation

The Tsuji-Trost reaction is the palladium-catalyzed allylation of nucleophiles with allylic compounds via π-allylpalladium complexes.

General features:

1. The reaction is regioselective. And unsymmetrical allyl substrates usually undergo substitution at the least hindered allylic position. But the selectivity also depends on the size of the nucleophile and the nature of the ligands employed. 2. The oxidative addition goes with inversion of configuration. Then, depending on the strength of the nucleophile, the reaction can take two different pathways. Soft nucleophiles normally add directly to the allyl moiety, whereas hard nucleophiles attack first the metal center. 3. As a rule of thumb, soft nucleophiles are those substrates that typically have conjugate acids with pKas lower than 25, while hard nucleophiles typically have conjugate acids with pKas greater than 25.