Fairlamb, Ian J.S. orcid.org/0000-0002-7555-2761, Lang, Jan, Růžička, Aleš et al. (2 more authors) (2023) Direct Cyclopalladation of Fluorinated Benzyl Amines by Pd3(OAc)6:The Coexistence of Multinuclear PdnReaction Pathways Highlights the Importance of Pd Speciation in C-H Bond Activation. Organometallics. ISSN 0276-7333
Abstract
Palladacycles are key intermediates in catalytic C-H bond functionalization reactions and important precatalysts for cross-couplings. It is commonly believed that palladacycle formation occurs through the reaction of a substrate bearing a C-H bond ortho to a suitable metal-directing group for interaction with, typically, mononuclear "Pd(OAc)2"species, with cyclopalladation liberating acetic acid as the side product. In this study, we show that N,N-dimethyl-fluoro-benzyl amines, which can be cyclopalladated either ortho or para to fluorine affording two regioisomeric products, can occur by a direct reaction of Pd3(OAc)6, proceeding via higher-order cyclopalladated intermediates. Regioselectivity is altered subtly depending on the ratio of substrate:Pd3(OAc)6 and the solvent used. Our findings are important when considering mechanisms of Pd-mediated reactions involving the intermediacy of palladacycles, of particular relevance in catalytic C-H bond functionalization chemistry.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | Funding Information: The University of Pardubice, Royal Society (Industry Fellowship to I.J.S.F.) and EPSRC (grant number EP/S009965/1) are acknowledged for financial support. We are very grateful to the University of York for hosting a research visitor position for J.V. (2019; hosted by I.J.S.F.) and to Prof. RN Perutz for initial discussions concerning this research. I.J.S.F. acknowledges the Royal Society for an Industry Fellowship. Publisher Copyright: © 2023 The Authors. Published by American Chemical Society. |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 27 Jul 2023 11:20 |
Last Modified: | 16 Oct 2024 19:20 |
Published Version: | https://doi.org/10.1021/acs.organomet.3c00178 |
Status: | Published online |
Refereed: | Yes |
Identification Number: | 10.1021/acs.organomet.3c00178 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:201938 |
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Filename: acs.organomet.3c00178.pdf
Description: DirectCyclopalladationof FluorinatedBenzylAminesby Pd3(OAc)6:The Coexistenceof MultinuclearPdnReactionPathwaysHighlightsthe Importanceof Pd Speciationin C−H BondActivation
Licence: CC-BY-NC 2.5