In our previous report, the oxidation p-bromothiophenol with organo-iodanes PIDA (1.0 equiv in CHCl3, 3h) or IBX (1.0 equiv in MeCN, 2h) afforded the homo-coupled product, i.e., disulfide, in 84 and 92% yields, respectively. PIDA is a λ 3 -iodane with iodine at +3 oxidation state, whereas the iodine is at +5 oxidation state for IBX. Considering the oxidation states, the oxidation with more electron-deficient λ iodane, i.e., IBX, should be superior to the PIDA, and one can expect further oxidation of disulfide to thiosulfonates. However, while the reactivities of both iodanes remained similar that produced disulfide selectively, no thiosulfonate was observed from the reaction of IBX and thiol. It might be due to the poor solubility of IBX and its reduced product, i.e., oiodosobenzoic acid (IBA, λ 3 -iodane). It is worth mentioning that IBX is not soluble in common organic solvents except polar and high-boiling DMSO. To facilitate further oxidation of the in situ generated disulfide to thiosulfonate in common organic solvents, we carried out the reactions with the soluble triacetate derivative of IBX, i.e., DMP. The oxidation of p-bromothiophenol (1b), as a representative case, was optimized using DMP in different solvents like DCM, dichloroethane (DCE), AcOH, acetone, MeOH, DMSO and DMF, at rt (~30 °C), cf. Table . The reactions with DMP (1.2 equiv) in DCM and DMF gave the desired thiosulfonate 2b in >81% yields (entries 2 and 10, respectively), whereas in other solvents, bis(4-bromophenyl)disulfide (3b) was obtained as the major product. The reaction with only 1.2 equiv of DMP suggests that the in situ produced λ 3 -iodane, from the reduction of DMP, also participates in the oxidation process. The reaction in methanol clearly indicates that the reduced λ 3 -iodane from DMP can promote oxidation of thiol to disulfide and/or thiosulfonate (entry 6) It is also noteworthy that no over-oxidation products, i.e., sulfonyl sulfoxide and/or disulfone, were formed when higher equivalents of DMP (2.4 equiv) was employed (entry 4). Encouraged by the facile oxidation with DMP, the oxidation of thiophenols with IBX in common organic solvent was reinvestigated. It is worth mentioning that IBX is a very mild oxidant that remains unreactive towards various electronrich and oxidizable groups like aldehyde, ketone, alkene, alkyne, pyridine, sulfide, thiophene, furan, iodoarene, acetal, N-Boc, N-Cbz, etc. Thus, the oxidation protocol could be very beneficial in terms of functional group tolerance.