A methodology campaign cannot continue without access to the requisite test substrates. Fortunately, for homoallylic sulfamates, allylic sulfamides, and homoallylic sulfamides, standard Prilezhaev oxidation conditions allowed for reliable access to the desired epoxides (Scheme 2A). Allylic sulfamates are not stable to synthesis and isolation. Thus, allylic alcohols were first converted into the corresponding epoxides, and the sulfamate auxiliary was subsequently appended using the Johnson-Magolan protocol (Scheme 2B). Our first attempts at tethered ring-opening with a pendant sulfamate were informed by our previous work with di-tert-butylsilanol auxiliaries. In sharp contrast to our past experience, treatment of sulfamate A with either Lewis acids ( We were next interested in exploring the effects of various N-substituents on reaction performance (Scheme 3). Our optimized protocol of 1 equivalent of Bu4NOH in a biphasic solvent mixture of CF3toluene/H2O worked nicely with NH2-sulfamate 1 and N-Me-sulfamate 3 (Scheme 3, Entries 1-2). With N-Et-sulfamate 5, the reaction time had to be extended to 48 hours for full consumption of the starting material (Scheme 3, Entry 3). Bulkier substituents on the sulfamate nitrogen (Scheme 3, Entries 4-5), required us to abandon NBu4OH in favor of 1M aqueous NaOH. With N-Bn-sulfamate 7, an extended reaction time of 48 hours was required for optimal product formation using 1M aqueous NaOH in Et2O (Scheme 3, Entry 4). With N-p-methoxyphenyl-sulfamate 9, optimal product formation occurred with 1M aqueous NaOH in CF3-toluene at an elevated reaction temperature of 45 °C. Finally, the reaction invariably failed with N-cyclohexyl-sulfamate 11 over a range of conditions. From this series of experiments, we conclude that the cyclization is quite sensitive to substituents on the sulfamate nitrogen. In addition, as the steric bulk increases, switching from Bu4NOH to NaOH is required, and elevating the reaction temperature is beneficial in some cases.