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

The energetically-favorable coordination of aldehydes and ketones - but not esters or amides - to Ni-0 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 pi-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 Ni-0. This work advances our understanding of how common functional groups interact with Ni-0 catalysts and how these interactions affect workhorse catalytic reactions in academia and industry.