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Related Reactions
Hosomi-Sakurai Reaction
Allylic Substitutions
Synthesis of allylamines
Substitution of active methylenes

Tsuji-Trost Reaction
Trost Allylation

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:

A. Leitner, C. Shu, J. F. Hartwig, Org. Lett., 2005, 7, 1093-1096.

Recent Literature

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Chiral Phosphine-Free Pd-Mediated Asymmetric Allylation of Prochiral Enolate with a Chiral Phase-Transfer Catalyst
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Deracemization of Baylis-Hillman Adducts
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Catalytic Enone Cycloallylation via Concomitant Activation of Latent Nucleophilic and Electrophilic Partners: Merging Organic and Transition Metal Catalysis
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A series of trialkylsilylated chiral aminophosphine ligands are prepared from (S)-prolinol and applied to a palladium-catalyzed asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate with a dimethyl malonate-BSA-LiOAc system.
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Development of (Trimethylsilyl)ethyl Ester Protected Enolates and Applications in Palladium-Catalyzed Enantioselective Allylic Alkylation: Intermolecular Cross-Coupling of Functionalized Electrophiles
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Allylic Aminations with Hindered Secondary Amine Nucleophiles Catalyzed by Heterobimetallic Pd-Ti Complexes
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