The reductive cleavage of the carbon - oxygen bond of aryl- and arylmethyl alkyl ethers by electron transfer from alkali metals in ethereal solvents was utilized to generate aryl- and arylmethyl carbanions. This procedure was successfully extended to different classes of alkoxy-substituted aromatic compounds, including derivatives of aldehydes and ketones and heterocyclic compounds, thus allowing the generation of functionalized carbanions. Such carbanions were trapped with different; electrophiles under mild reaction conditions, and the overall process is a reductive electrophilic substitution of the alkoxy group. The usefulness of this reaction is illustrated with several examples, including the syntheses of natural products and pharmacologically active compounds.