Synthesis of allylamines
Substitution of active methylenes
The Tsuji-Trost Reaction is the palladium-catalyzed allylation of nucleophiles such as active methylenes, enolates, amines and phenols with allylic compounds such as allyl acetates and allyl bromides.
Mechanism of the Tsuji-Trost Reaction
The coordination of the Pd(0)-catalyst to the double bond forms an η2 π-allyl complex. An oxidative addition, during which the leaving group is expelled, gives an η3 π-allyl complex. This step is also called ionization:
Depending on the strength of the nucleophile, the reaction can take two different pathways. Soft nucleophiles, such as those derived from conjugate acids with a pKa < 25, normally add directly to the allyl moiety, whereas hard nucleophiles first attack the metal center, followed by reductive elimination to give the allylation product:
These two mechanistic modes have an impact on the development of asymmetric variants of the Tsuji-Trost Reaction. For a discussion, see a recent review by Trost and Vranken (Chem. Rev., 1996, 96, 395. DOI).
Nonsymmetric allyl substrates normally undergo substitution at the least hindered allylic position, with a selectivity that depends on the size of the nucleophile:
Sterically unhindered nucleophiles such as phenol give the more branched product.
Similar reactions can be conducted using catalysts based on molybdenum or iridium. These reactions offer - as an alternative to the Tsuji-Trost Reaction - access to branched regioisomers:
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