Many catalytic reactions are improved (accelerated or made more selective) by Lewis or Bronsted acidic additives, but mechanistic roles can be difficult to ascertain. A few vignettes are presented to highlight approaches to deciphering the subtle, complex roles additives may play in organotransition metal catalysis. Palladium C-N and C-C bond formations are found to be accelerated by the addition of Lewis acids; the additive accelerates turnover-limiting transmetalation, perhaps by influencing Pd-halide equilibria. In another example, Mo-catalyzed Z-selective isomerization is becomes faster with added p-Toluenesulfonic acid, which may aid the dissociation of phosphine or generate Mo-H species in situ.

Applications and mechanisms of external Lewis and Bronsted acid additives in organotransition metal chemistry

256th National Meeting (2018)

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