Direct Substitution of Aromatic Ethers by Lithium Amides. A New Aromatic Amination Reaction

Article abstract of DOI:10.1021/jo00071a019

Reaction of lithiated dialkylamines with methoxy aromatics in refluxing THF leads to products resulting from a direct ipso-substitution.Especially with lithiated secondary amines high conversions and selectivities are achieved.Sulfonyl-substituted aromatics react equally well, but halogenated aromatics give rise to side-products arising from a competing pathway via aryne intermediates.The scope and mechanistic implications of this novel nucleophilic amination reaction are described.