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The nickel-catalyzed carboxylation of organic halides or pseudohalides using carbon dioxide is an emerging method to prepare synthetically valuable carboxylic acids. Here, we report a detailed mechanistic investigation of these reactions using the carboxylation of aryl halides with (PPh 3 ) 2 Ni II Cl 2 as a model reaction. Our studies allow us to understand several general features of nickel-catalyzed carboxylation reactions. For example, we demonstrate that both a Lewis acid and halide source are beneficial for catalysis. To this end, we establish that heterogeneous Mn(0) and Zn(0) reductants are multifaceted reagents that generate noninnocent Mn(II) or Zn(II) Lewis acids upon oxidation. In a key result, a rare example of a well-defined nickel(I) aryl complex is isolated, and it is demonstrated that its reaction with carbon dioxide results in the formation of a carboxylic acid in high yield (after workup). The carbon dioxide insertion product undergoes rapid decomposition, which ca These three oxidation states correspond to the onbe circumvented by a ligand metathesis reaction with a halide source. Our studies have led to both a revised mechanism and the development of a broadly applicable strategy to improve reductive carboxylation reactions. A critical component of this strategy is that we have replaced the heterogeneous Mn(0) reductant typically used in catalysis with a well-defined homogeneous organic reductant. Through its use, we have increased the range of ancillary ligands, additives, and substrates that are compatible with the reaction. This has enabled us to perform reductive carboxylations at low catalyst loadings. Additionally, we demonstrate that reductive carboxylations of organic (pseudo)halides can be achieved in high yields in more practically useful, non-amide solvents. Our results describe a mechanistically guided strategy to improve reductive carboxylations through the use of a homogeneous organic reductant, which may be broadly translatable to a wide range of cross-electrophile coupling reactions.

Development of an Improved System for the Carboxylation of Aryl Halides through Mechanistic Studies