Nucleophilic addition versus migratory insertion pathways in the gold-catalysed Heck reaction: A computational study

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Budzelaar, Peter H. M., Rocchigiani, Luca and Bochmann, Manfred (2025) Nucleophilic addition versus migratory insertion pathways in the gold-catalysed Heck reaction: A computational study. Chemistry – A European Journal, 31 (41). ISSN 0947-6539

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Abstract

The initial reaction steps in the formation of Heck-type arylated alkenes catalyzed by P^N chelated Au(III) complexes have been studied computationally. Two mechanistic alternatives have been explored: (1) alkene coordination and insertion into a gold-carbon bond, and (2) nucleophilic attack on a gold(III) alkene adduct. The common starting point, the [(P^N)AuPh(alkene)] 2+ dication (alkene = C 2H 4, H 2C═CHEt, or H 2C═CEt 2), shows unequal bonding to the olefinic carbons of the 1-alkenes (P^N = 1,2-C 6H 4NMe 2(PR 2); R = H, Me, 1-adamantyl). This polarization increases with steric hindrance and with the inclusion of an OTf - anion in the model. While the reaction pathways are strongly governed by the trans-influence of the ligand, the effects of steric hindrance in the ligand and alkene are remarkably small. In all cases the nucleophilic attack pathway is energetically favored. However, changing the ligand from a P^N to a P^P chelate, with a strongly electron-donating -PMe 2 donor trans to Ph, sufficiently destabilizes the Au─Ph bond to make alkene insertion competitive. Alkene 1,2-insertion regiochemistry is always preferred, unlike Pd-catalyzed Heck reaction that requires a 2,1-insertion. Based on these results, an alkene insertion pathway en route to Heck-type olefins can therefore be ruled out.

Item Type: Article
Additional Information: Data Availability Statement: The data that support the findings of this study are available in the supplementary material of this article. Funding information: LR is grateful to the Royal Society of Chemistry (R22-0875640255) and for financial support by a European Union–NextGenerationEU National Innovation Ecosystem grant ECS00000041–VITALITY under the Italian Ministry of University and Research (MUR). MB thanks the Leverhulme Trust for an Emeritus Fellowship (EM-2024–028∖4).
Uncontrolled Keywords: dft,catalysis,chelate ligands,gold,mechanisms,chemistry(all),catalysis,organic chemistry ,/dk/atira/pure/subjectarea/asjc/1600
Faculty \ School: Faculty of Science > School of Chemistry, Pharmacy and Pharmacology
UEA Research Groups: Faculty of Science > Research Groups > Chemistry of Materials and Catalysis
Faculty of Science > Research Groups > Chemistry of Light and Energy
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Depositing User: LivePure Connector
Date Deposited: 30 Jun 2025 11:30
Last Modified: 06 Aug 2025 10:30
URI: https://ueaeprints.uea.ac.uk/id/eprint/99777
DOI: 10.1002/chem.202501645

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