The [1, 3] O-to-C rearrangement: opportunities for stereoselective synthesis

Abstract

The relay of stereochemistry of a breaking C-O bond into a forming C-C bond is well-known in the context of [3, 3] sigmatropic shifts; however, this useful strategy is less well-known in other types of molecular rearrangements. Though the first successful example of a [1, 3] O-to-C rearrangement was reported more than 100 years ago, this class of reactions has received less attention than its [3, 3] counterpart. This perspective analyzes the various methods used for the activation and [1, 3] rearrangement of vinyl ethers with an emphasis on mechanism and applications to stereoselective synthesis. We also highlight our own contributions to this area.