Rapid and Scalable Halosulfonylation of Strain‐Release Reagents**

Sulfonylated aromatics are commonplace motifs in drugs and agrochemicals. However, methods for the direct synthesis of sulfonylated non-classical arene bioisosteres, which could improve physicochemical properties drug agrochemical candidates, limited. Here we report a solution to this challenge: one-pot halosulfonylation [1.1.1]propellane, [3.1.1]propellane bicyclo[1.1.0]butanes that proceeds under practical, scalable mild conditions. The sulfonyl halides used chemistry feature aryl, heteroaryl alkyl substituents, conveniently generated situ from readily available sulfinate salts halogen atom sources. This methodology enables an array pharmaceutically agrochemically relevant halogen/sulfonyl-substituted bioisosteres cyclobutanes, on up multidecagram scale.