Unravelling mechanistic insights in the platinum-catalysed dihydroalkoxylation of allenes

Quiros Lopez, Maria, Gomez-Bengoa, Enrique and Munoz-Herranz, Maria Paz ORCID: https://orcid.org/0000-0001-9037-349X (2020) Unravelling mechanistic insights in the platinum-catalysed dihydroalkoxylation of allenes. Pure and Applied Chemistry, 92 (1). pp. 167-177. ISSN 0033-4545

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Abstract

The mechanism of the platinum-catalysed dihydroalkoxylation of allenes to give acetals has been studied experimentally and by computational methods. Our findings further explain divergent reactivity encountered for platinum- and gold-vinyl intermediates after the first nucleophilic attack onto the coordinated allene, as well as provide new details on the catalytic cycle with platinum, uncovering enol ethers as resting states of the catalytic cycle, a S(E)Ox process via Pt(V)-H as the final protodemetallation step after the second nucleophilic attack when neutral platinum complexes are used, and a fast acid promoted addition of methanol to enol ethers when cationic platinum complexes are employed.

Item Type: Article
Uncontrolled Keywords: activation,allylic ethers,chemistry,complexes,dynamic solution behavior,gold catalysis,gold(i)-catalyzed intermolecular hydroalkoxylation,hydroamination,icpoc-24,protonolysis,pt-c bond,allenes,catalysis,gold,hydroalkoxylation,mechanism,platinum
Faculty \ School: Faculty of Science > School of Chemistry
UEA Research Groups: Faculty of Science > Research Groups > Chemistry of Materials and Catalysis
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Depositing User: LivePure Connector
Date Deposited: 17 Jan 2020 04:09
Last Modified: 22 Oct 2022 05:29
URI: https://ueaeprints.uea.ac.uk/id/eprint/73670
DOI: 10.1515/pac-2019-0214

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