Uncatalyzed Meerwein-Ponndorf-Oppenauer-Verley Reduction of Aldehydes and Ketones under Supercritical Conditions

Lena Sominsky, Esther Rozental, Hugo Gottlieb, Aharon Gedanken, Shmaryahu Hoz

Research output: Contribution to journalArticlepeer-review

41 Scopus citations

Abstract

When a solution of a carbonyl compound in alcohol (primary or secondary) is heated to ca. 300 °C, a disproportionation reaction, in which a carbonyl compound is reduced to the corresponding alcohol and the alcohol is oxidized to the corresponding ketone, takes place. This uncatalyzed variation of the Meerwein-Ponndorf-Oppenauer-Verley reaction gives, in certain cases, e.g., reduction of acetophenone or benzaldehyde by i-PrOH, almost quantitative yields. Yields are higher with secondary alcohols such as i-PrOH than with a primary alcohol such as EtOH. The reactions were also performed in a flow system by passing at a slow rate the same solutions through a glass or a metal coil heated to elevated temperatures. Ab initio calculations performed at the B3LYP/6-31G* level show that thermodynamically i-PrOH is a more potent reducing agent than EtOH by ca. 4 kcal/mol. The computations also show that in cases of aromatic carbonyl compounds, part of the deriving force is obtained from the entropy change of the reaction. The major contributor to the high yield, however, is the excess alcohol used, which shifts the equilibrium to the right. Calculated entropy of activation as well as isotopic H/D labeling suggest a cyclic transition state.

Original languageEnglish
Pages (from-to)1492-1496
Number of pages5
JournalJournal of Organic Chemistry
Volume69
Issue number5
DOIs
StatePublished - 5 Mar 2004

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