In summary, we have developed scalable methods for the regioselective C-2 dehydration of sugar thioacetals. The resulting dithioketene acetals are versatile synthetic intermediates which can be used to access polyols containing a stereogenic centre bearing an ethyl group. Preliminary studies have also demonstrated that the dithioketene acetal activates the C-3 hydroxyl group for further selective dehydration reactions, and cyclisation of these compounds can be used to access chiral heterocycles (THFs, butyrolactones) that are useful building blocks for asymmetric synthesis.