Synthesis of Alkyl (ortho-Benzyl)-Aryl Sulfoxides Enabled by Truce-Smiles Rearrangement

An atom-economical and chemoselective synthesis of alkyl (ortho-benzyl)-aryl sulfoxides has been developed. Sulfenate anions, which were generated by the Truce-Smiles rearrangement of heteroaryl (ortho-alkyl)-aryl sulfoxides, have been trapped by primary alkyl halides to deliver the corresponding sulfoxides. A Truce-Smiles rearrangement/cyclization cascade has been designed to expand the scope of secondary cycloalkyl sulfoxides.