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:

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.

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.

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.