Unravelling mechanistic insights in the platinum-catalysed dihydroalkoxylation of allenes

Quiros Lopez, Maria and Gomez-Bengoa, Enrique and Munoz-Herranz, Maria Paz (2019) 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:
Journal Article
Journal or Publication Title:
Pure and Applied Chemistry
Uncontrolled Keywords:
Research Output Funding/yes_externally_funded
Subjects:
?? activationallylic etherschemistrycomplexesdynamic solution behaviorgold catalysisgold(i)-catalyzed intermolecular hydroalkoxylationhydroaminationicpoc-24protonolysispt-c bondallenescatalysisgoldhydroalkoxylationmechanismplatinumyes - externally fundednoge ??
ID Code:
185707
Deposited By:
Deposited On:
03 Feb 2023 16:20
Refereed?:
Yes
Published?:
Published
Last Modified:
16 Jul 2024 11:59