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Hf(OTf) 4 was identified as a highly potent catalyst (0.1-0.5 mol%) for three-component Mannich reaction under solvent-free conditions. Hf(OTf) 4 -catalyzed Mannich reaction exhibited excellent regioselectivity and diastereoselectivity when alkyl ketones were employed as substrates. 1 H NMR tracing of the H/D exchange reaction of ketones in MeOH- d  4 indicated that Hf(OTf) 4 could significantly promote the keto-enol tautomerization, thereby contributing to the acceleration of reaction rate.

Hf(OTf)4 as a Highly Potent Catalyst for the Synthesis of Mannich Bases under Solvent-Free Conditions