AbstractThe tris(formamidinato)lanthanum(III) complexes [La(o‐TolForm)3(thf)2] [1; o‐TolForm = N,N′‐bis(o‐tolyl)formamidinate], [La(XylForm)3(thf)] [2; XylForm = N,N′‐bis(2,6‐dimethylphenyl)formamidinate], and [La(EtForm)3] [3, EtForm = N,N′‐bis(2,6‐diethylphenyl)formamidinate] are a new class of precatalysts for the Tishchenko reaction. Their catalytic activity is a result of their high Lewis acidity and the ease with which the ligand spheres can be interchanged. For the dimerization of benzaldehyde to give benzyl benzoate, which is a benchmark reaction, compound 1 is, to the best of our knowledge, the most active catalyst ever reported. On a preparative scale, the reaction can be performed in the absence of solvent. A range of aromatic, heteroaromatic, and aliphatic aldehydes was rapidly converted into the corresponding esters by using catalysts 1–3.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)