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Tsuji-Trost Reaction

(Tsuji-Trost Allylation, Tsuji-Trost Allylic Substitution, Tsuji Allylation)

Published Online: 15 SEP 2010

DOI: 10.1002/9780470638859.conrr630

Comprehensive Organic Name Reactions and Reagents

Comprehensive Organic Name Reactions and Reagents

How to Cite

2010. Tsuji-Trost Reaction. Comprehensive Organic Name Reactions and Reagents. 630:2812–2816.

Publication History

  1. Published Online: 15 SEP 2010

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Abstract

The mild synthesis of allylic compounds via palladium catalyzed allylic alkylation of activated nucleophiles is generally known as the Tsuji–Trost reaction. In this reaction, the allylic moiety is often activated by means of allyl halide, acetate, or carbonate, and the nucleophile originating from aldehyde or ketone is used in the form of corresponding enolates, silyl enolates, or enamines. Although the reaction often employs Pd(0) complexes, it is reported that olefins can be directly converted into π-allyl palladium complexes in high yields by the treatment with either PdCl2/Na2CO3 in CH2Cl2 or PdCl2/NaCl/NaAc in acetic acid. It has been reported that attacking the η3 allyl (or π-allyl) palladium complex, the allylation of nucleophiles can occur at position 1 or 3 of the allylic moiety; however, due to the steric hindrance, most of the reported allylations take place at the less-substituted termini. The study finds that the electronic nature of nucleophiles can alter the regioselectivity if the reaction. This reaction has wide application in organic synthesis, especially in the conversion of allyl β-ketoesters into β-allyl ketones.

Keywords:

  • cycloalkanones;
  • Lewis acid;
  • regioselectivity;
  • π-allyl palladium complexes