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In this review, a personal account of our work in the field of hypervalent iodine reagents is presented. Pioneering experiments, which led to the discovery of the exceptional reactivity of EthynynnnlBenziodoXol( on)e (EBX) reagents as electrophilic alkyne synthons is first discussed, including the alkynylation of ketoesters, olefins and heterocycles. Our further work involving EBX reagents in domino reactions and the alkynylation of thiols, as well as the use of benziodoxole reagents for azidation reactions is then described. Finally, the most recent results involving radicals and carbenes as reaction partners for EBX reagents and their first use in chemical biology are presented. The purpose of this review is not to give an extensive overview of our results, but to show the 'true story' beyond the discovery by presenting the most important pioneering experiments. Failed attempts and near misses are also briefly discussed.

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