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Ozonolysis of 1,4-cyclohexadienes in the presence of methanol and acid. Mechanism and intermediates in the conversion of 1,4-cyclohexadiene derivatives to beta-keto esters



Ozonolysis of 1,4-cyclohexadienes in the presence of methanol and acid. Mechanism and intermediates in the conversion of 1,4-cyclohexadiene derivatives to beta-keto esters



Journal of Organic Chemistry 69(12): 4135-4139



Conditions for the preparation of beta-keto esters directly from 1,4-cyclohexadiene derivatives are described. This procedure is a further step in the application of the synthetic methodology, which consists of the combination of Birch reduction of available benzene derivatives followed by ozonolysis. In this work, the syntheses of derivatives of dimethyl gamma-keto-alpha-aminoadipate and dimethyl beta-keto glutamate from the corresponding 1,4-cyclohexadiene derivatives are described. The latter compounds are prepared from phenylalanine and phenylglycine, respectively. The study of the ozonolysis of simple alkyl derivatives of 1,4-cyclohexadiene in the presence of methanol, both in the presence and absence of acid, helped to establish the mechanism of this reaction. The proximity of the two double bonds, which are cleaved, leads to the intermediate formation of 1,2-dioxolane derivatives that could be identified by NMR spectroscopy. It is shown that regardless of the regioselectivity of the cleavage of the primary ozonide, which is formed, all 1,2-dioxolane derivatives can lead to beta-keto esters. This is due to the equilibrium between these dioxolanes in the presence of methanol and acid.

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Accession: 049839724

Download citation: RISBibTeXText

PMID: 15176839

DOI: 10.1021/jo049731y


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