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.

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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.

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Recent Literature

Direct Catalytic Intermolecular α-Allylic Alkylation of Aldehydes by Combination of Transition-Metal and Organocatalysis
I. Ibrahem, A. Córdova, Angew. Chem. Int. Ed., 2006, 45, 1952-1956.

Catalytic Enone Cycloallylation via Concomitant Activation of Latent Nucleophilic and Electrophilic Partners: Merging Organic and Transition Metal Catalysis
B. G. Jellerich, J.-R. Kong, M. J. Krische, J. Am. Chem. Soc., 2003, 125, 7758-7759.

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.
Y. Tanaka, T. Mino, K. Akita, M. Sakamoto, T. Fujita, J. Org. Chem., 2004, 69, 6679-6687.

Deracemization of Quaternary Stereocenters by Pd-Catalyzed Enantioconvergent Decarboxylative Allylation of Racemic β-Ketoesters
J. T. Mohr, D. C. Behenna, A. M. Harned, B. M. Stoltz, Angew. Chem. Int. Ed., 2005, 44, 6924-6927.

P-Chirogenic Diaminophosphine Oxide: A New Class of Chiral Phosphorus Ligands for Asymmetric Catalysis
T. Nemoto, T. Matsumoto, T. Masuda, T. Hitomi, K. Hatano, Y. Hamada, J. Am. Chem. Soc., 2004, 126, 3690-3691.

Easy Access to Esters with a Benzylic Quaternary Carbon Center from Diallyl Malonates by Palladium-Catalyzed Decarboxylative Allylation
D. Imao, A. Itoi, A. Yamazaki, M. Shirakura, R. Ohtoshi, K. Ogata, Y. Ohmori, T. Ohta, Y. Ito, J. Org. Chem., 2007, 72, 1534-1537.

Water Enables Direct Use of Allyl Alcohol for Tsuji-Trost Reaction without Activators
H. Kinoshita, H. Shinokubo, K. Oshima, Org. Lett., 2004, 6, 4085-4088.

1-Phosphino-2-sulfenylferrocenes as Planar Chiral Ligands in Enantioselective Palladium-Catalyzed Allylic Substitutions
O. G. Mancheno, J. Priego, S. Cabrera, R. G. Arrayas, T. Llamas, J. C. Carretero, J. Org. Chem., 2003, 68, 3679-3686.

Asymmetric Claisen Rearrangements Enabled by Catalytic Asymmetric Di(allyl) Ether Synthesis
S. G. Nelson, K. Wang, J. Am. Chem. Soc., 2006, 128, 4232-4233.

Palladium-Triethylborane-Triggered Direct and Regioselective Conversion of Allylic Alcohols to Allyl Phenyl Sulfones
S. Chandrasekhar, V. Jagadeshwar, B. Saritha, C. Narsihmulu, J. Org. Chem., 2005, 70, 6506-6507.

Palladium-Catalyzed Dehydrative Allylation of Hypophosphorous Acid with Allylic Alcohols
K. Bravo-Altamirano, J.-L. Montchamp, Org. Lett., 2006,8, 4169-4171.