Since monosubstituted BCBs have been employed as covalent modifiers (Scheme 1B), we subjected compound 3 to a glutathione (GSH) stability assay. We found no GSH conjugation upon incubation at 37 °C with NADPH (see Supporting Information). We have demonstrated a convenient two-step procedure for the synthesis of substituted BCBs from commercially available starting materials. First, 1-iodo-3-substituted-BCPs are generated by a mild decarboxylative iodination reaction promoted by simple CFL irradiation at ambient temperature. The corresponding iodo-BCPs can then be transformed to substituted BCBs upon reaction with primary and secondary amines or aliphatic thiols in sulfolane. Microwave heating at high temperatures (130-140 °C) for less than 1 hour affords substituted BCB products in similar yields as heat block reactions at 80 °C for several days. We hope that this transformation can be used to expand the collection of BCB derivatives as sp rich carbocyclic cores.