title: Double [3,3]-sigmatropic rearrangement in the enzymatic dioxygenation of benzyl azide: preparation of novel synthetically valuable azido-diols.
abstract: 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.
authors: Departamento de Química Orgánica and ‡Departamento Estrella Campos, Facultad de Química - Universidad de la República , General Flores 2124, CP 11800, Montevideo, Uruguay.
authors: Natalia
authors: N
authors: Thevenet
authors: Victoria
authors: V
authors: de la Sovera
authors: María Agustina
authors: MA
authors: Vila
authors: Nicolás
authors: N
authors: Veiga
authors: David
authors: D
authors: Gonzalez
authors: Gustavo
authors: G
authors: Seoane
authors: Ignacio
authors: I
authors: Carrera
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis* / Q000737:chemistry; D001386:Azides / Q000737:chemistry*; D015394:Molecular Structure; D010105:Oxygenases / Q000378:metabolism*; D013237:Stereoisomerism
chemical_list: D000438:Alcohols; D001386:Azides; D010105:Oxygenases; C023172:toluene dioxygenase