Surprisingly, the reactions of benzyl thiols 1ln with DMP led to benzyl 2-iodobenzoates 4ln in 6983% isolated yields; the reactions were found to be very slow (48h). Contrarily, the reaction of 1l with 2.0 equiv of IBX selectively produced S-benzyl benzylsulfonothioate 2l in 73% yield, Scheme 2. Generally, such benzyl-esterification with λ 3 -iodane is observed for the reactions of ethynylbenziodoxolones (EBX) with thiiranes and thiethanes, the photochemical-cum-metal-catalyzed reaction of IBA with styrene, and arylacetic acid with several λ 3 -iodanes. However, to the best of our knowledge, the transfer of an iodoarene from a hypervalent iodine(V) compound, i.e., λ 5iodane, is unprecedented. This protocol can thus serve as one-pot functional group transformation of benzyl thiols to alcohols. It is worth mentioning that the conversion of alcohols to thiols are known using Lawesson's reagent and through Newmann-Kwart rearrangement, however, a methodology that serve for one-pot thiol to alcohol is still at large. Herein, the reactions of benzyl thiols 1ln with DMP led to benzoate esters 4ln in 6978% isolated yield in 48h, Scheme 2. The isolated product 4l was hydrolyzed with aqueous 1M NaOH that offered benzyl alcohol 5l with overall yield with 67%, Scheme 2. Further study on the mechanistic details and their applicability in organic synthesis is going on in our lab. It is to be noted that reaction of benzyl thiol 1l with IBX was consistent with other thiols that offered thiosulfonate 2l in 73% yields; no benzoate ester was observed.