Herein, for the first time we have explored the umpolung reactivity of vinylogous carbon center of diazo arylidene succinimide (DAS) through rhodium catalysis to achieve [2,3]-Stevens rearrangement of α-thioether esters. The protocol has successfully demonstrated the distal C-H bond functionalization of the α-thioether esters. Alongside, the carbenoid reactivity of DAS has also been achieved with Doyle-Kirmse reaction of allyl/propargyl phenyl sulfides. The protocol proved to be practical to synthesize a wide variety of [2,3]-Stevens rearrangement products exclusively and the possible side products emanating from Pummerer rearrangement and [1,2]-Stevens rearrangement were not observed. This catalytic protocol works smoothly in environmentally benign solvent under open air to afford the corresponding desired products with excellent diastereo-, regio- and chemo-selectivities in good to excellent yields. The protocol also proved to be scalable on gram quantity.