Celebrating 20 Years of SYNLETT-Special Account On the Merits of Biocatalysis and the Impact of Arene cis-Dihydrodiols on Enantioselective Synthesis

This account is a tribute to Professor David Gibson in recognition of his discovery of enzymatic dihydroxylation of aromatic compounds four decades ago. Here are highlighted some of the milestones in microbiology, biochemistry, molecular biology, and synthetic organic chemistry connected with this unique reaction. Gibson's discovery greatly contributed to advancing biocatalysis as a discipline with major impact on synthesis of optically pure compounds. Personal recollections of several chemists who have embraced this technology in their own work, along with the authors' recollections of the early days of research involving the cis-dihydrodiols, are provided as Notes at the end of the article. 1 Introduction: History of Biocatalysis 2 The Discovery of Enzymatic Dihydroxylation 3 Processing of Arenes by Oxidoreductase Enzymes 4 Considerations of the Mechanism 5 Diversity of Metabolites 6 cis-Dihydrodiols as Synthetic Intermediates: Analysis of Reactivity and Symmetry Options 7 Historically Important Milestones in Applications to Synthesis 8 Outlook 9 Notes