Neighboring Heteroatom Effect Unique to Aqueous Aldol Reactions of Water-Insoluble Substrates

Abstract

The reactions of ketones and aldehydes in the presence of Li(+) and in the presence or absence of PTC mediated by water were performed to produce aldol products. Several advantages of the aqueous reactions over organic solvent-mediated ones have been demonstrated including higher yields, shorter reaction times, simpler purifications, and better functional group tolerance. Some reactions that do not take place in organic solvents have been realized in water. The successes are attributed to the neighboring heteroatom effect. In the aqueous aldol condensations, Li2CO3 was an efficient catalyst, and therefore base-liable groups such as epoxides, esters, and silyl groups could survive. For heteroaromatic ethanones, the aqueous aldol reactions were accomplished without PTC to give β-hydroxyketones in good yields. The water-mediated condensations of aldosyl hemiacetals with aromatic ketones led to a new carbohydrate-derived skeleton in quantitative yields. To some extent, this research has expanded the applicablities of aldol condensations and reactions.