Double [3,3]-Sigmatropic Rearrangement in the Enzymatic Dioxygenation of Benzyl Azide: Preparation of Novel Synthetically Valuable Azido-diols Natalia Thevenet Victoria de la Sovera María Agustina Vila Nicolás Veiga David Gonzalez Gustavo Seoane Ignacio Carrera 10.1021/ol503708v.s001 https://acs.figshare.com/articles/journal_contribution/Double_3_3_Sigmatropic_Rearrangement_in_the_Enzymatic_Dioxygenation_of_Benzyl_Azide_Preparation_of_Novel_Synthetically_Valuable_Azido_diols/2208964 Enzymatic dioxygenation of benzyl azide by toluene dioxygenase produces the expected enantiopure <i>cis</i>-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. 2015-02-06 00:00:00 optimized production protocol sequence Sigmatropic Synthetically sigmatropic rearrangements dioxygenation diol moiety toluene dioxygenase exocyclic diene product synthesis benzyl azide Preparation protection Rearrangement novel dienediol shift Valuable enantiopure Enzymatic Dioxygenation Benzyl Azide