Oxidative decarboxylative coupling (ODC) reactions offer an attractive route to generate functionalized arenes from widely available and inexpensive carboxylic acid coupling partners, yet they are under utilized due to limitations in the scope of benzoic acids. In many such reactions only <i>ortho-</i>nitrobenzoic acids undergo efficient coupling. Silver salts are commonly employed as stoichiometric oxidants in these reactions and are also often responsible for the decarboxylation step. Through the systematic study of a series of well-defined silver carboxylate complexes, we have identified the role of the <i>ortho</i>-substituent in the decarboxylation of benzoates by silver. We have found that a single parameter, the field effect, governs the rate of decarboxylation. Our efforts to use this finding to improve the synthetic scope of related catalytic ODC reactions will also be presented.

Predictive model for the rates of decarboxylation of silver benzoate complexes relevant to catalytic decarboxylative coupling reactions

255th National Meeting (2018)

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