Tishchenko Reaction

Abstract The disproportionation of nonenolizable aldehydes to form corresponding esters in the presence of aluminum alkoxide or sodium alkoxide is known as the Tishchenko reaction. Besides the Tishchenko reaction, the present study also discusses the Tishchenko reduction and the Evans‐Tishchenko reaction. Furthermore, combination of the reversible aldol reaction and the irreversible Tishchenko reaction is generally known as the aldol‐Tishchenko reaction. Besides the aluminum alkoxides and sodium alkoxides that are usually used to affect the Tishchenko reaction, many other molecules or complexes have been found to effectively promote the Tishchenko reaction. It has been reported that the aldol‐Tishchenko reaction, exhibiting a large inverse equilibrium isotope effect and can be catalyzed by different catalysts. It has been noticed that the SmI 2 ‐catalyzed Evans‐Tishchenko reaction always gives trans ‐1,3‐diol monoester via a chelation‐controlled pathway. The combination of an aldol reaction and the Tishchenko reaction to form adjacent three or five stereocenters of high diastereoselectivity is also an important modification, which may be catalyzed by using the monoalcoholate of 1,3‐diols. In addition, the Tishchenko reaction has been successfully performed in supercritical carbon dioxide.