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HOMOGENEOUS CATALYSIS

β-Elimination rules for Pd

Nature Synthesis volume 1, pages 753–754 (2022)Cite this article

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β-Hydride and β-heteroatom eliminations are competitive processes in many Pd-catalysed reactions but general strategies for controlling this selectivity have not been established. Now, a mechanistic study of Pd-alkyl complexes demonstrates that the choice of phosphine ligands and leaving groups controls selectivity.

β-Elimination processes are fundamental steps in many transition metal-catalysed reactions but are challenging to control. In these processes, either a β-hydride (H) or a β-heteroatom group (X) of a metal-alkyl complex migrates to the metal centre with concurrent formation of a C=C double bond1. These β-H and β-X elimination processes typically compete with each other because many metal-alkyl complexes can bear both a hydrogen and a heteroatom on the same β-carbon atom. Controlling these competing β-H and β-X elimination reactions is important for a variety of industrial processes. For example, promoting β-H elimination drives Mizoroki–Heck reactions2, because this step allows the metal to disengage the substrate. In contrast, avoiding unproductive β-H and β-X elimination pathways is key for C(sp3)–C(sp3) cross-coupling and haloalkene polymerization reactions, respectively3.

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Fig. 1: The effects of β-migrating groups and ligands on competing β-heteroatom (β-X) and β-hydride (β-H) eliminations.

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  1. Twitter: @Altmaniacs

Authors and Affiliations

  1. The Scripps Research Institute, La Jolla, CA, USA

    Ming-Hsiu Yang

  2. Purdue University, West Lafayette, IN, USA

    Ryan A. Altman

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  1. Ming-Hsiu Yang
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  2. Ryan A. Altman
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Correspondence to Ryan A. Altman.

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The authors declare no competing interests.

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Yang, MH., Altman, R.A. β-Elimination rules for Pd. Nat. Synth 1, 753–754 (2022). https://doi.org/10.1038/s44160-022-00144-y

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