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Aldehydes and Ketones Influence Reactivity and Selectivity in Nickel-Catalyzed Suzuki-Miyaura Reactions

preprint
submitted on 18.02.2019 and posted on 19.02.2019 by Alasdair Cooper, David Leonard, Sonia Bajo, Paul Burton, David Nelson
We show that the energetically-favorable coordination of aldehydes and ketones – but not esters – to nickel(0) during Suzuki-Miyaura reactions can lead either to exquisite selectivity and enhanced reactivity, or to the inhibition
of the reaction. Aryl halides where the C-X bond is connected to the same π-system as an aldehyde or ketone functional
group undergo unexpectedly rapid oxidative addition, and are selectively cross-coupled during inter- and intramolecular
competition reactions. When aldehydes and ketones are present elsewhere, such as in the form of exogenous additives,
the cross-coupling reaction is inhibited depending on how strongly the pendant carbonyl group can coordinate to nickel(0). This work advances our understanding of how common functional groups interact with nickel(0) catalysts, and presents synthetic chemists with a tool that can be used to achieve site-selectivity in functionalized molecules.

Funding

Understanding Mechanism and Selectivity in Oxidative Addition to Nickel(0) for Catalytic Cross Coupling

Engineering and Physical Sciences Research Council

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Industrial CASE Account - University of Strathclyde 2016

Engineering and Physical Sciences Research Council

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West of Scotland Supercomputing Centre for Academia and Industry (Capital)

Engineering and Physical Sciences Research Council

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History

Email Address of Submitting Author

david.nelson@strath.ac.uk

Institution

University of Strathclyde

Country

United Kingdom

ORCID For Submitting Author

0000-0002-9461-5182

Declaration of Conflict of Interest

No conflict of interest

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