Double [3,3]-Sigmatropic Rearrangement in the Enzymatic Dioxygenation of Benzyl Azide: Preparation of Novel Synthetically Valuable Azido-diols

Enzymatic dioxygenation of benzyl azide by toluene dioxygenase produces the expected enantiopure cis-cyclohexadienediol along with an exocyclic diene formed by a spontaneous sequence of two [3,3] sigmatropic shifts. This novel dienediol presents high synthetic potential for natural product synthesis. The sigmatropic rearrangements can be reversed by protection of the diol moiety. An optimized production protocol for either of these valuable diols is presented.