The chemistry of mesoionic rings, especially their use as masked dipoles, has been a fruitful area of research since the late 1950s. With recent advances in the control of regio- and stereochemistry, the dipolar cycloaddition led to widespread application. In this Account, we illustrate our contribution employing thioisomünchnones, a class of mesoionics that has found use in creating a series of heterocyclic systems hitherto inaccessible by conventional 1,3-dipolar cycloaddition. We also provide some rationalizations from computations and comment on future directions.