A process for preparing a sucrose-6-ester, a key intermediate to sucralose. The process contains (a) reacting sucrose with a di(hydrocarbyl)tin oxide or a 1,3-diacyloxy-1,1,3,3-tetra(hydrocarbyl)distannoxane in the presence of a secondary alcohol and an organic polar aprotic solvent, to prepare a mixture comprising 1,3-di-(6-O-sucrose)-1,1,3,3-tetra(hydrocarbyl)distannoxane and the secondary alcohol; and (b) adding an acylating agent to the mixture, thereby acylating the 1,3-di-(6-O-sucrose)-1,1,3,3-tetra(hydrocarbyl)distannoxane to prepare a sucrose-6-ester.