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Reactions of dimedone and alkyl orthoformates with and without activators

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Abstract

The experimental and theoretical studies of the reactions of 5,5-dimethylcyclohexane-1,3-dione (dimedone) with trimethyl- and triethyl orthoformates under various conditions were carried out. It was demonstrated that in the absence of activators the reactions of substrate with ortho esters proceed exclusively as C-C coupling, and in the presence of Brønsted (H2SO4) or Lewis (BF3·Et2O) acids the formation of both C-C and C-O coupling products is observed. The energy consumptions of all reactions in accordance with proposed mechanisms were estimated using quantum chemical calculations by the B3LYP/6-311++G(d,p) method in terms of PCM/MeCN.

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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, Russia

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

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  1. V. L. Novikov
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  2. V. P. Glazunov
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  3. N. N. Balaneva
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  4. O. P. Shestak
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Correspondence to O. P. Shestak.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2241–2254, October, 2022.

No human or animal subjects were used in this research.

The authors declare no competing interests.

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Novikov, V.L., Glazunov, V.P., Balaneva, N.N. et al. Reactions of dimedone and alkyl orthoformates with and without activators. Russ Chem Bull 71, 2241–2254 (2022). https://doi.org/10.1007/s11172-022-3652-6

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