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Catalytic nucleophilic 'umpoled' π-allyl reagents.

Kim Spielmann1, Gilles Niel, Renata Marcia de Figueiredo

  • 1Institut Charles Gerhardt Montpellier (ICGM), UMR 5253, Univ Montpellier, CNRS, ENSCM - Ecole Nationale Supérieure de Chimie, 8, Rue de l'Ecole Normale, 34296 Montpellier Cedex 5, France. jean-marc.campagne@enscm.fr.

Chemical Society Reviews
|January 12, 2018
PubMed
Summary

Researchers explored the

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Area of Science:

  • Organic Chemistry
  • Catalysis
  • Synthetic Methodology

Background:

  • The Tsuji-Trost reaction, a cornerstone of palladium-catalyzed allylation, traditionally employs π-allyl intermediates as electrophiles.
  • The concept of reversing π-allyl intermediate reactivity (acting as nucleophiles) has been explored since the 1980s.
  • Achieving controlled regioselectivity, diastereoselectivity, and enantioselectivity is crucial for complex molecule synthesis.

Purpose of the Study:

  • To highlight the concept of 'umpoled' reactivity of π-allyl intermediates.
  • To showcase recent advancements in catalytic enantioselective allylation utilizing this reversed reactivity.
  • To demonstrate the impact of these methods on natural product and drug synthesis.

Main Methods:

  • Utilizing various transition metal sources to facilitate the nucleophilic character of π-allyl intermediates.

Related Experiment Videos

  • Modifying the electronic environment of metal catalysts through additives and ligands.
  • Application of these methodologies in the enantioselective allylation of carbonyl compounds and imines.

    • Main Results:

    • Demonstrated a powerful 'reactivity switch' for π-allyl intermediates, enabling nucleophilic behavior.
    • Achieved high levels of regio-, diastereoselectivity, and enantioselectivity in allylation reactions.
    • Provided efficient catalytic methods with significant implications for complex molecule synthesis.

    Conclusions:

    • The 'umpoled' reactivity of π-allyl intermediates offers a versatile strategy in organic synthesis.
    • Catalytic enantioselective allylation using nucleophilic π-allyl intermediates is a key enabling technology.
    • These advancements significantly impact the efficient construction of natural products and drug candidates.