Science of Synthesis

Yan, L.; Lin, S.; Liu, P., Science of Synthesis, (2007) 20, 745.

The homo aldol–Tishchenko reaction involves the trimerization of enolizable aldehydes. Under the reaction conditions, 2 equivalents of an aldehyde undergo condensation to form an aldol adduct ‌58‌, which is subsequently reduced by a third equivalent of the aldehyde to yield a mixture of 1,3-diol monoesters ‌59‌ and ‌60‌ (‌Scheme 20‌).[‌65‌] As in the classic Tishchenko procedure intramolecular hydride transfer is the rate-limiting step, but the reaction is highly catalyst dependent. Traditional catalysts with high basicity or low acidity favor the aldol–Tishchenko reaction [such catalysts, include 2,4,6-trimethylphenoxymagnesium bromide,[‌66‌,‌67‌] SmI2,[‌68‌] Sm(Cp*)2(THF)2,[‌69‌,‌70‌] LiOiPr, LiWO2,[‌71‌] BINOL-Li,[‌72‌] and Y5O(O-iPr)13].

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References