We have developed a scalable and column chromatography free synthesis of a protected 4thioribose intermediate. This synthetic methodology has also been adapted for a multigram preparation of 2-deoxy-2-gem-difluoro 4-thioribose analogues. These building blocks enable entry to a range of pyrimidine-based 4'-thionucleoside analogues, including first examples of 4'-sulfinyl derivatives of ribocytidine, Ara-C and gemcitabine.