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Mechanism of catalytic migration of the double bond in 2-vinylnorbornanes

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Abstract

Liquid-phase hydrogenation of 5-vinylbicyclo[2.2.1]hept-2-ene (5-vinyl-2-norbornene, VNE) existing as a mixture of endo- and exo-isomers in the presence of a palladium catalyst (0.25% Pd/γ-Al2O3, or PC-25) is a complex consecutive-parallel process proceeding via the formation of (endo/exo)-2-vinylnorbornanes. Subsequent hydrogenation of the latter is preceded by quantitative isomerization of the vinyl group to the ethylidene one. The mechanism of the phenomenon was studied experimentally and theoretically. It was established that isomerization of 2-vinylnorbornanes to 2-ethylidenenorbornanes requires the presence of palladium (as the active component of the catalyst) and hydrogen in the reaction system. All reaction products were identified and the material balance of the process was studied. According to DFT PBE/SBK quantum chemical calculations, migration of the multiple bond in 2-vinylnorbornanes on the Pd(111) face of the model cluster Pd21(H)2 is of allylic character.

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Funding

This work was carried out using the equipment of the Center for Collective Use of the Russian Technological University MIREA, supported by the Ministry of Science and Higher Education of the Russian Federation under Contract No. 075-15-2021-689 dated September 01, 2021.

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Authors and Affiliations

  1. M. V. Lomonosov Institute of Fine Chemical Technologies, MIREA - Russian Technological University, 86 prosp. Vernadskogo, 119571, Moscow, Russia

    V. V. Zamalyutin, R. S. Shamsiev & V. R. Flid

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  1. V. V. Zamalyutin
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  2. R. S. Shamsiev
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  3. V. R. Flid
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Corresponding authors

Correspondence to V. V. Zamalyutin or V. R. Flid.

Additional information

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2142–2148, October, 2022.

No human or animal subjects were used in this research.

The authors declare no competing interests.

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Zamalyutin, V.V., Shamsiev, R.S. & Flid, V.R. Mechanism of catalytic migration of the double bond in 2-vinylnorbornanes. Russ Chem Bull 71, 2142–2148 (2022). https://doi.org/10.1007/s11172-022-3639-3

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  • DOI: https://doi.org/10.1007/s11172-022-3639-3

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