Aldehydes and ketones influence reactivity and selectivity in nickel-catalysed Suzuki-Miyaura reactions

Alasdair K. Cooper, David K. Leonard, Sonia Bajo, Paul M. Burton, David J. Nelson

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Abstract

The energetically-favorable coordination of aldehydes and ketones – but not esters or amides – to Ni0 during Suzuki-Miyaura reactions can lead either to exquisite selectivity and enhanced reactivity, or to inhibition of the reaction. Aryl halides where the C-X bond is connected to the same π-system as an aldehyde or ketone undergo unexpectedly rapid oxidative addition to [Ni(COD)(dppf)] (1), and are selectively cross-coupled during competition reactions. When aldehydes and ketones are present in the form of exogenous additives, the cross-coupling reaction is inhibited to an extent that depends on the strength of the coordination of the pendant carbonyl group to Ni0. This work advances our understanding of how common functional groups interact with Ni0 catalysts and how these interactions affect workhorse catalytic reactions in academia and industry.
Original languageEnglish
Number of pages7
JournalChemical Science
Early online date6 Jan 2020
DOIs
Publication statusE-pub ahead of print - 6 Jan 2020

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Nickel
Ketones
Aldehydes
Amides
Functional groups
Esters
Catalysts
Industry

Keywords

  • aldehyde3s
  • ketones
  • aryl halides

Cite this

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abstract = "The energetically-favorable coordination of aldehydes and ketones – but not esters or amides – to Ni0 during Suzuki-Miyaura reactions can lead either to exquisite selectivity and enhanced reactivity, or to inhibition of the reaction. Aryl halides where the C-X bond is connected to the same π-system as an aldehyde or ketone undergo unexpectedly rapid oxidative addition to [Ni(COD)(dppf)] (1), and are selectively cross-coupled during competition reactions. When aldehydes and ketones are present in the form of exogenous additives, the cross-coupling reaction is inhibited to an extent that depends on the strength of the coordination of the pendant carbonyl group to Ni0. This work advances our understanding of how common functional groups interact with Ni0 catalysts and how these interactions affect workhorse catalytic reactions in academia and industry.",
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Aldehydes and ketones influence reactivity and selectivity in nickel-catalysed Suzuki-Miyaura reactions. / Cooper, Alasdair K.; Leonard, David K.; Bajo, Sonia; Burton, Paul M.; Nelson, David J.

In: Chemical Science, 06.01.2020.

Research output: Contribution to journalArticle

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T1 - Aldehydes and ketones influence reactivity and selectivity in nickel-catalysed Suzuki-Miyaura reactions

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AU - Leonard, David K.

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AU - Burton, Paul M.

AU - Nelson, David J.

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