New modes of reactivity in the threshold of the reduction potential in solution. Alkylation of lithium PAH (polycyclic aromatic hydrocarbon) dianions by primary fluoroalkanes: a reaction pathway complementing the classical birch reductive alkylation.

Some of the most highly reduced organic species in solution, such as the dianions of PAHs (polycyclic aromatic hydrocarbons) display unexpected reactivity patterns when they react with an appropriate counterpart. As seen before in their reaction with propene and other alkenes, PAHs(-2) apparently react with fluoroalkanes in a nucleophilic fashion in spite of being generally regarded as powerful electron-transfer reagents in their reactions with haloalkanes. This methodology complements the current methodologies on reductive alkylation of polycyclic arenes by allowing access to a new set of regioisomers, the regiochemistry of which can be easily predicted by simple MO calculations.