| Sumario: | Glycols and ethoxy– and propoxy–alcohols are fundamental chemicals in industry, with annual productions of millions of tons, still manufactured in many cases with corrosive and unrecoverable catalysts such as KOH, amines and BF•OEt. Here we show that commercially available, inexpensive, non–toxic, solid and recyclable nanotitania catalyzes the hydration and alkoxylation of epoxides, with water and primary and secondary alcohols but not with phenols, carboxylic acids and tertiary alcohols. In this way, the chemoselective synthesis of different glycols and 1,4–dioxanones, and the implementation of nanotitania for the production in–flow of glycols and alkoxylated alcohols, has been achieved. Mechanistic studies support the key role of vacancies in the nano–oxide catalyst.
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