Meyer, S, Göbel, L, Livingstone, K orcid.org/0000-0002-4169-3056 et al. (3 more authors) (2022) Cyclopropene activation via I(I)/I(III) catalysis: Proof of principle and application in direct tetrafluorination. Tetrahedron, 126. 132925. ISSN 0040-4020
Abstract
Preliminary validation of cyclopropene activation by an I(I)/I(III) catalysis manifold is disclosed to enable the direct tetrafluorination of 3,3-diarylcyclopropenes. This transformation occurs through the in situ generation of ArI(III)F2, with inexpensive iodobenzene, amine·HF complexes and Selectfluor® serving as catalyst, fluoride source and oxidant, respectively. Leveraging this approach, it has been possible to generate four C(sp3)-F bonds in a single operation (up to 44%). A Hammett study revealed that the reaction has a very narrow tolerance window with respect to the p-substituent of the aryl groups. Through a process of reaction deconstruction, a mechanism involving two discrete catalytic processes is proposed. Whereas the first cycle results in the ring opening fluorination of the 3,3-diarylcyclopropene, the second proceeds via a fluorination/phenonium ion rearrangement to liberate a tetrafluorinated diarylethane. This study adds hypervalent iodine catalysis to the plenum of strategies that facilitate cyclopropene activation.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/). |
Keywords: | Cyclopropene; Fluorination; Iodine catalysis; Organocatalysis; Structural analysis |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Organic Chemistry (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 04 Apr 2023 09:37 |
Last Modified: | 04 Apr 2023 09:37 |
Status: | Published |
Publisher: | Elsevier |
Identification Number: | 10.1016/j.tet.2022.132925 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:197941 |