Double deprotonation of pyridinols generates potent organic electron donor initiators for haloarene-arene coupling

Transition metal-free couplings of haloarenes with arenes, triggered by the use of alkali metal alkoxides in the presence of an organic additive, are receiving significant attention in the literature. Most of the known organic additives effect coupling of iodoarenes, but not bromoarenes, to arenes. Recently Kwong showed that 2-pyridinecarbinol 11 extends the reaction to aryl bromides. This paper
investigates the mechanism, and reports evidence for dianions derived from 11 as electron donors to initiate the reaction. It also proposes routes by which electron-poor benzoyl derivatives can be transformed into electron donors to initiate these reactions.