Tishchenko Reaction—a nucleophilic substitution reaction

In 1887, L. Claisen discovered the formation of benzyl benzoate from the reaction of benzaldehyde in the presence of sodium alkoxides. Almost thirty years later, W.E. Tishchenko found that both enolizable and non-enolizable aldehydes could be converted to their corresponding esters in the presence of magnesium or aluminum alkoxides, and this became known as the Tishchenko Reaction. The most common catalysts used are aluminum alkoxides, but a wide variety of other catalysts can be used, including alkali- and alkali—earth metal oxides and alkoxides, transition metal-based catalysts such as ruthenium complexes, and certain rhodium, iridium, and iron complexes.

The most widely used modification to the Tishchenko reaction is the Evans-Tishchenko reaction that transforms a chiral betahydroxy ketone in the presence of an aldehyde and catalytic samarium iodide (SmI2) into the anti-1,3-diol monoester with excellent diastereoselectivity.

The natural product Rhizoxin D, a potent antitumor and antifungal compound, was synthesized utilizing the Evans-Tishchenko reaction.

The Tishchenko and Evans-Tishchenko reactions