Chiral, air stable, and reliable Pd(0) precatalysts applicable to asymmetric allylic alkylation chemistry

Jingjun Huang, Thomas Keenan, François Richard, Jingru Lu, Sarah E. Jenny, Alexandre Jean, Stellios Arseniyadis () and David C. Leitch ()
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Jingjun Huang: University of Victoria, Department of Chemistry
Thomas Keenan: Queen Mary University of London, Department of Chemistry
François Richard: Queen Mary University of London, Department of Chemistry
Jingru Lu: University of Victoria, Department of Chemistry
Sarah E. Jenny: Temple University, Department of Chemistry
Alexandre Jean: Industrial Research Centre, Oril Industrie
Stellios Arseniyadis: Queen Mary University of London, Department of Chemistry
David C. Leitch: University of Victoria, Department of Chemistry

Nature Communications, 2023, vol. 14, issue 1, 1-12

Abstract: Abstract Stereoselective carbon-carbon bond formation via palladium-catalyzed asymmetric allylic alkylation is a crucial strategy to access chiral natural products and active pharmaceutical ingredients. However, catalysts based on the privileged Trost and Pfaltz-Helmchen-Williams PHOX ligands often require high loadings, specific preactivation protocols, and excess chiral ligand. This makes these reactions uneconomical, often unreproducible, and thus unsustainable. Here we report several chiral single-component Pd(0) precatalysts that are active and practically-applicable in a variety of asymmetric allylic alkylation reactions. Despite the decades-long history and widespread use of Trost-type ligands, the precatalysts in this work are the only reported examples of stable, isolable Pd(0) complexes with these ligands. Evaluating these precatalysts across nine asymmetric allylic alkylation reactions reveals high reactivity and selectivity at low Pd loading. Importantly, we also report an unprecedented Pd-catalyzed enantioselective allylation of a hydantoin, achieved on gram scale in high yield and enantioselectivity with only 0.2 mol% catalyst.

Date: 2023
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DOI: 10.1038/s41467-023-43512-8

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