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Activator-free reactions of carboxylic ortho esters with cyclic β-diketones

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Abstract

The reaction mechanisms of cyclic 1,3-diketones with trialkyl orthoformates and trimethyl orthoacetate in the absence of activators were theoretically and experimentally studied. The reactions proceed via C-C-coupling of the ionized forms of the reactants giving dialkyl acetals, which further transform into vinyl ethers. The reactions of the latter with ortho esters afford aldehydes (ketones). Related 2-acetylcyclopentanone reacts with trimethyl orthoacetate under argon to form a mixture of methyl enol ethers, whereas in the presence of air oxygen dimethyl glutarate is formed.

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Authors and Affiliations

  1. G. B. Elyakov Pacific Institute of Bioorganic Chemistry, Far-East Branch of Russian Academy of Sciences, 159 prosp. 100 Let Vladivostoku, 690022, Vladivostok, Russian Federation

    N. N. Balaneva, O. P. Shestak, V. L. Novikov & V. P. Glazunov

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  1. N. N. Balaneva
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  2. O. P. Shestak
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  3. V. L. Novikov
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This paper does not contain descriptions of studies on animals or humans.

The authors declare no competing interests.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1584–1598, August, 2021.

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Balaneva, N.N., Shestak, O.P., Novikov, V.L. et al. Activator-free reactions of carboxylic ortho esters with cyclic β-diketones. Russ Chem Bull 70, 1584–1598 (2021). https://doi.org/10.1007/s11172-021-3255-7

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