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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


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.


Regioselective Single-Electron Tsuji-Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach
Z.-J. Wang, S. Zheng, E. Romero, J. K. Matsui, G. A. Molander, Org. Lett., 2019, 21, 6543-6547.


A Pd(0)-Catalyzed Direct Dehydrative Coupling of Terminal Alkynes with Allylic Alcohols To Access 1,4-Enynes
Y.-X. Li, Q.-Q. Xuan, L. Liu, D. Wang, Y.-J. Chen, C.-J. Li, J. Am. Chem. Soc., 2013, 135, 12536-12539.


Raising the pKa Limit of "Soft" Nucleophiles in Palladium-Catalyzed Allylic Substitutions: Application of Diarylmethane Pronucleophiles
S.-C. Sha, J. Zhang, P. J. Carroll, P. J. Walsh, J. Am. Chem. Soc., 2013, 135, 17602-17609.


Chiral Phosphine-Free Pd-Mediated Asymmetric Allylation of Prochiral Enolate with a Chiral Phase-Transfer Catalyst
M. Nakoji, T. Kanayama, T. Okino, Y. Takemoto, Org. Lett., 2001, 3, 3329-3331.


Deracemization of Baylis-Hillman Adducts
B. M. Trost, H.-C. Tsui, F. D. Toste, J. Am. Chem. Soc., 2000, 122, 3534-3535.


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.


Development of (Trimethylsilyl)ethyl Ester Protected Enolates and Applications in Palladium-Catalyzed Enantioselective Allylic Alkylation: Intermolecular Cross-Coupling of Functionalized Electrophiles
C. M. Reeves, D. C. Behenna, B. M. Stoltz, Org. Lett., 2014, 16, 2314-2317.


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.


Formal α-Allylation of Primary Amines by a Dearomative, Palladium-Catalyzed Umpolung Allylation of N-(Aryloxy)imines
L. M. Mori-Quiroz, S. S. Londhe, M. D. Clift, J. Org. Chem., 2020, 85, 14827-14846.


Aerobic Allylic Amination Catalyzed by a Pd(OAc)2/P(OPh)3 System with Low Catalyst Loading
T. Yurino, S. Saito, M. Ichihashi, T. Ohkuma, J. Org. Chem., 2022, 87, 2864-2872.


Palladium Nanoparticle-Catalyzed C-N Bond Formation. A Highly Regio- and Stereoselective Allylic Amination by Allyl Acetates
L. Adak, K. Chattopadhyay, B. C. Ranu, J. Org. Chem., 2009, 74, 3982-3985.


Allylic Aminations with Hindered Secondary Amine Nucleophiles Catalyzed by Heterobimetallic Pd-Ti Complexes
W. K. Walker, D. L. Anderson, R. W. Stokes, S. J. Smith, D. J. Michaelis, Org. Lett., 2015, 17, 752-755.


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.


Catalytic α-Allylation of Unprotected Amino Acid Esters
P. Fang, M. R. Chaulagian, Z. D. Aron, Org. Lett., 2012, 14, 2130-2133.


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.


Palladium/TY-Phos-Catalyzed Asymmetric Heck/Tsuji-Trost Reaction of o-Bromophenols with 1,3-Dienes
Y. Tu, B. Xu, Q. Wang, H. Dong, Z.-M. Zhang, J. Zhang, J. Am. Chem. Soc., 2023, 145, 4378-4383.