Products Cited in Publications Worldwide From alkenylboronates to enynes: ligand and activator-driven pathways in nickel-catalyzed alkyne functionalization

From alkenylboronates to enynes: ligand and activator-driven pathways in nickel-catalyzed alkyne functionalization

Gruszczyński, Marcin; Lewandowski, Dariusz; Kuciński, Krzysztof; Kubicki, Maciej; Hreczycho, Grzegorz

DOI:

Abstract

Nickel catalysis provides opportunities to modulate reaction pathways through changes in the coordination environment, yet strategies to deliberately redirect nickel reactivity remain limited. Here we show that ligand exchange at nickel allows a single catalytic system to produce different products from the same alkyne substrates. Aminophosphine-supported nickel catalysts promote selective hydroboration in the presence of pinacolborane, which functions both as a boron source and a reaction activator. The addition of forms a distinct ligand-coordinated nickel species that suppresses hydroboration and directs the reaction toward enyne formation. Our further studies identify coordination as a key step that directs the catalytic cycle, illustrating how simple additives can influence reaction outcomes. These results offer a straightforward strategy to access divergent reactivity in nickel catalysis and provide insight into the factors controlling catalytic pathway selection.

Keywords

Alkynes ; Nickel catalysis ; Ligand effects ; Hydroboration ; Enynes

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