Hafnium Trifluoromethanesulfonate [Hf(OTf)4] as a Unique Lewis Acid in Organic Synthesis

This microreview summarizes examples of Hf(OTf)(4)-mediated or -catalyzed organic reactions. Hafnium triflate possesses four strongly electron-withdrawing OTf groups, together with an ionic radius of intermediate range (Al < Ti < Hf, Zr < Sc < Ln), and has an oxophilic hard character typical of group IV metals. This Lewis acid shows outstanding performance in catalytic Friedel-Crafts acylation reactions and Mannich-type reactions of imines, hydrazones, and N,O-acetals. Several natural products have also been synthesized by use of Hf(OTf)(4)-mediated or -catalyzed reactions. Moreover, Hf(OTf)(4) has a number of potent features in carbohydrate syntheses. Hf(OTf)(4) possesses many unique characteristics that distinguish it from other Lewis acids. The unique characteristics of Hf(OTf)(4) should make this compound a major candidate for selection as a Lewis acid in the future.