Taher, EhabBanwell, MartinBuckler, JoshuaYan, QiaoLan, Ping2021-01-071528-0691http://hdl.handle.net/1885/219215The title compounds of the general form 1 can be produced at large scale and in essentially enantiomerically pure form (when X≠H) through the whole cell biotransformation of the corresponding aromatic. The “dense” and varied functionality associated with these metabolites mean that they have become increasingly useful chirons for the total synthesis of a range of natural product types. This personal account details the outcomes of a nearly three‐decade long campaign within our group to exploit these compounds in the synthesis of a diverse range of small molecule natural product targets. The work is subdivided according to the key transformation(s) employed in each synthesis. The development of newer chirons that “complement” the utility of the cis‐1,2‐dihydrocatechols are also described.We thank the Australian Research Council, the Institute of Advanced Studies at the Australian National University, the Islamic Development Bank, the China Scholarship Council and Circa Pty Ltd (Melbourne) for generous financial support. The invaluable contributions of our colleagues who co-authored the articles listed below are also gratefully acknowledged.application/pdfen-AU© 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimChironsCross-couplingsDiels-Alder Reactionscis-1,2-DihydrocatecholsElectrophilic AdditionsEschenmoser-Claisen rearrangementsNatural ProductsOxidative Cleavage201810.1002/tcr.2017000642020-11-23