Mechanism of copper-free Sonogashira reaction operates through palladium-palladium transmetallation
作者： Martin Gazvoda , Miha Virant , Balazs Pinter , Janez Košmrlj
DOI: 10.1038/S41467-018-07081-5
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摘要: The seminal contributions by Sonogashira, Cassar and Heck in mid 1970s on Pd/Cu- Pd-catalysed (copper-free) coupling of acetylenes with aryl or vinyl halides have evolved myriad applications. Despite the enormous success both academia industry, however, critical mechanistic questions this cross-coupling process remain unresolved. In study, experimental evidence computational support is provided for mechanism copper-free Sonogashira reaction. contrast to consensus monometallic mechanism, revealed pathway proceeds through a tandem Pd/Pd cycle linked via multistep transmetallation process. This virtually identical Pd/Cu copper co-catalysed cross-couplings, but role CuI played set PdII species. Phosphine dissociation from square-planar reactants form transient three-coordinate Pd species initiates represents rate-determining step
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