Aromatic Claisen Rearrangements of Benzyl Ketene Acetals: Conversion of Benzylic Alcohols to (ortho-Tolyl)acetates.

Claisen rearrangements of benzyl vinyl ethers are much less facile than those of aliphatic allyl vinyl ethers, and their synthetic utility has remained relatively unexplored. A one-pot procedure is reported for the generation and Claisen rearrangement of benzyl vinyl ethers that contain an activating α-alkoxy substituent on the vinyl group. A [3,3]-sigmatropic mechanism was supported by trapping of the intermediate isotoluene in an intramolecular Alder-ene reaction. [ABSTRACT FROM AUTHOR]