Achievements, Challenges, and Scope of Thirty Years of Work on the Biotransformation of Arenes and Their Synthetic Applications

This account describes the results of three decades of work on the production, chemistry, and synthetic applications of cis-cyclohexadienediols obtained by biotransformation of arenes. These cis-diols are valuable chiral building blocks, as they are enantiomerically pure, possessing good accessibility and high chemical versatility. Our work covers enzymatic and chemical aspects of the biotransformation, as well as synthetic applications of the resulting cis-diols. We optimized the biotransformation procedure, described a computational model of TDO, designed new mutants, identified new metabolites, and disclosed new reactions of the Rieske dioxygenases. Also, the reactivity of the cis-diol core was studied, with an emphasis in addition reactions, such as cycloadditions, osmylations, and electrophilic additions. Preparation of building blocks and bioactive natural products is described from the synthetic point of view, mostly concerning cyclitols, carbasugars, acetogenin and carbohydrates.