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Understanding the thermal [1s,5s] hydrogen shift isomerization of ocimene

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Abstract

α-Ocimene, β-ocimenes and alloocimenes are isomeric monoterpenes occurring naturally as oils within several plants and fruits. These thermally unstable compounds are employed in the pharmaceutical and fine-chemicals industries due to their natural plant defense properties and pleasant odors. In this work, and in the context of a recent revival in attention on the subject, we provide new theoretical insights concerning the nature of the electronic reorganization driving the decomposition of cis-β-ocimene to alloocimene. Our findings support the experimental proposal of a rearrangement via a six-membered cyclic transition state in a one-step concerted and highly synchronic process.

Thermal isomerization of ocimene; two transition structures are feasible considering the relative position (equatorial or axial) of the bulky isobutenyl group at carbon C5

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Acknowledgments

We are grateful for the continuous support provided by Fondecyt (Chile) grant numbers 1140343 (EC), and 11130589 (MD-N), the Millennium Science Initiative Nucleus No. 120082 (Chile), and the Universidad Nacional de Colombia grant 201010011033-DIME 2012 (Modalidad 2). E.C. thanks the Universidad Andres Bello (UNAB) for continuous support through research grant No. DI-219-12/N (Núcleo CIMFQ).

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Authors and Affiliations

  1. Departamento de Ciencias Químicas, Universidad Andres Bello, Avenida Republica 275, 8370146, Santiago, Chile

    Eduardo Chamorro & Mario Duque-Noreña

  2. Laboratorio de Fisicoquímica Orgánica, Facultad de Ciencias, Universidad Nacional de Colombia, Ap, 3840, Medellín, Colombia

    Pablo Ruiz, Jairo Quijano, Diana Luna, Laura Restrepo & Sandra Zuluaga

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  1. Eduardo Chamorro
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  2. Pablo Ruiz
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  3. Jairo Quijano
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  4. Diana Luna
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  7. Mario Duque-Noreña
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Correspondence to Eduardo Chamorro.

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ESM 1

Optimized Cartesian coordinates for reactant and products corresponding to the thermal rearrangement of ocimene to alloocimene via TS1-e, and TS1-a, obtained at the M05-2X/6-31G(d) level of theory. This material is available in Online Resource 1 (ESM_1.pdf). (DOCX 1017 kb)

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Chamorro, E., Ruiz, P., Quijano, J. et al. Understanding the thermal [1s,5s] hydrogen shift isomerization of ocimene. J Mol Model 20, 2390 (2014). https://doi.org/10.1007/s00894-014-2390-6

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