A new class of iminosulfonylation reagents were developed and extensively used in the 1,2-iminosulfonylation of various olefins. Olefins containing bioactive molecules, such as indomethacin, gemfibrozil, clofibrate, and fenbufen, afforded the desired iminosulfonylation products in synthetically useful yields. Furthermore, the first remote 1,6-iminosulfonylation of alkenes was realized by using oxime ester bifunctionalization reagents. Overall, more than 40 structurally diverse β-imine sulfones were obtained in moderate to excellent yields.