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The [(dppe)RhCl]‐catalysed ring expansion of 2‐methylbenzocyclobutenone has been proposed to occur by C−C oxidative addition to rhodaindanone, β‐hydride elimination, hydrorhodation and C−C reductive elimination. DFT calculations [IEFPCM(1,4‐dioxane, 383.15 K)/PBE0/DGDZVP level of theory] here confirm this mechanism. As proposed, oxidative addition into CHMe−CO bond is preferred over the alternative...
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