AbstractThe development of iodine(III)-mediated synthetic transformations has received growing interest, in particular to mediate enantioselective processes. In this class, the α-tosyloxylation of ketone derivatives using iodine(III) is a particularly powerful one, as it yields α-tosyloxy ketones – versatile chiral precursors that enable rapid access to numerous α-chiral ketones through nucleophilic displacement. Despite years of research from numerous groups, the enantioselectivities for this transformation have remained modest. Using quantum chemical calculations, we have uncovered a possible rational for the lack of selectivity. With these computational insights, we have developed an alternative experimental strategy and achieved unprecedented levels of selectivities. Applying this newfound knowledge, we have recently developed a new method to access α-halo ketones from non-ketonic precursors.