The reaction of the chiral auxiliary version of the Burgess reagent with epoxides yields diastereomeric pairs of sulfamidates, which lead to cis and trans amino alcohols in each enantiomeric series. Experimental and spectral details are provided for all new sulfamidates and the products derived from them. Structure revisions have been made for several previously reported products from the reactions of the Burgess reagent with cyclic oxiranes and styrene diols. Considerable revisions are also suggested for the possible mechanisms operating in the reactions of the Burgess reagent with 1,2‐diols and epoxides. Finally, a Density Functional Theory (DFT) study for the interaction of the achiral version of the Burgess reagent with oxiranes is included along with an explanation of the lack of asymmetric induction observed in reactions conducted in a catalytic mode with C2‐symmetric catalysts. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)