A methanesulfonylation reaction for the synthesis of sulfone-containing tetrasubstituted carbon stereocenters is described for the first time by simple treatment of indanedione-chromanone synthons with Et3N and easily accessible MsCl without any use of organometallic chemistry. This technology gave the corresponding valuable chromone-based 2-methanesulfonylated 1,3-indanediones in good yields (up to 89% yield) under mild conditions. The present work provides an attractive strategy for the construction of biologically interesting sulfone-containing tetrasubstituted carbon stereocenters, which might be valuable in medicinal chemistry.