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Rearrangements of 1-(1-methylprop-1-en-1-yl)-1,2-dimethylacenaphtyylenonium ions

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Abstract

It was discovered by means of dynamic NMR that the 1-(cis-1-methylprop-1-en-1-yl)-1,2-dimethylacenaphthylenonium ion generated under conditions of “long life” for carbocations underwent fast (ΔG#35.8 kJ mol−1 at −103°C) degenerate 1,2-shift of the cis-dimethylvinyl group. Quantum-chemical calculations by DFT method predict lower rate of 1,2-shift for the trans-dimethylvinyl group compared to cis-dimethylvinyl group and dependence on the cations conformation of the rates of these processes and of the rearrangement mechanism into the ions of phenalenyl type.

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Authors and Affiliations

  1. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk, 630090, Russia

    V. A. Bushmelev, A. M. Genaev & V. G. Shubin

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  1. V. A. Bushmelev
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  2. A. M. Genaev
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  3. V. G. Shubin
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Correspondence to A. M. Genaev.

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Original Russian Text © V.A. Bushmelev, A.M. Genaev, V.G. Shubin, 2006, published in Zhurnal Organicheskoi Khimii, 2006, Vol. 42, no. 2, pp. 236–242.

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Bushmelev, V.A., Genaev, A.M. & Shubin, V.G. Rearrangements of 1-(1-methylprop-1-en-1-yl)-1,2-dimethylacenaphtyylenonium ions. Russ J Org Chem 42, 220–226 (2006). https://doi.org/10.1134/S1070428002120102

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  • DOI: https://doi.org/10.1134/S1070428002120102

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