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An air- and moisture-stable ruthenium precatalyst for diverse reactivity

Research output: Contribution to Journal/MagazineJournal articlepeer-review

E-pub ahead of print
  • Gillian McArthur
  • Jamie H. Docherty
  • Mishra Deepak Hareram
  • Marco Simonetti
  • Iñigo J. Vitorica-Yrezabal
  • James J. Douglas
  • Igor Larrosa
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<mark>Journal publication date</mark>3/04/2024
<mark>Journal</mark>Nature Chemistry
Publication StatusE-pub ahead of print
Early online date3/04/24
<mark>Original language</mark>English

Abstract

Versatile, efficient and robust (pre)catalysts are pivotal in accelerating the discovery and optimization of chemical reactions, shaping diverse synthetic fields such as cross-coupling, C–H functionalization and polymer chemistry. Yet, their scarcity in certain domains has hindered the advancement and adoption of new applications. Here we present a highly reactive air- and moisture-stable ruthenium precatalyst [(tBuCN)5Ru(H2O)](BF4)2, featuring a key exchangeable water ligand. This versatile precatalyst drives an array of transformations, including late-stage C(sp2)–H arylation, primary/secondary alkylation, methylation, hydrogen/deuterium exchange, C(sp3)–H oxidation, alkene isomerization and oxidative cleavage, consistently outperforming conventionally used ruthenium (pre)catalysts. The generality and applicability of this precatalyst is exemplified through the potential for rapid screening and optimization of photocatalytic reactions with a suite of in situ generated ruthenium photocatalysts containing hitherto unknown complexes, and through the rapid discovery of reactivities previously unreported for ruthenium. The diverse applicability observed is suggestive of a generic platform for reaction simplification and accelerated synthetic discovery that will enable broader applicability and accessibility to state-of-the-art ruthenium catalysis.