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:
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.
A room temperature Pd-catalyzed allylic substitution of a wide range of soft nucleophiles derived from diarylmethane provides rapid access to the corresponding allylated products. A procedure for Pd-catalyzed allylic substitutions to afford diallylation products with quaternary centers is also described.
S.-C. Sha, J. Zhang, P. J. Carroll, P. J. Walsh, J. Am. Chem. Soc., 2013, 135, 17602-17609.
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.
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.
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.
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.