Palladium-catalyzed sabinene oxidation with hydrogen peroxide : smart fragrance production and DFT insights.
dc.contributor.author | Vieira, Camila Grossi | |
dc.contributor.author | Angnes, Ricardo Almir | |
dc.contributor.author | Braga, Ataualpa Albert Carmo | |
dc.contributor.author | Gusevskaya, Elena Vitalievna | |
dc.contributor.author | Rossi, Liane Marcia | |
dc.date.accessioned | 2023-05-17T20:12:25Z | |
dc.date.available | 2023-05-17T20:12:25Z | |
dc.date.issued | 2022 | pt_BR |
dc.description.abstract | Fragrance substances derived from natural sources are essential to the fine chemical industry, being an interesting task to pursue. Herein, we present a smart catalytic oxidation route for bio-renewable (1R,5R)-sabinene obtainment in acetonitrile or acetone, just using Pd(OAc)2 as catalyst and hydrogen peroxide as an final oxidant. The products obtained from (1R,5R)-sabinene and their mixtures have a distinct and pleasant smell and therefore are candidates for fragrance and pharmacological applications. Three oxyfunctionalized products were obtained with ca. 80% combined selectivity at high substrate conversions. The major products, two novel isomeric carane-type ketones with a bicyclo[4.1.0] skeleton, were formed by expanding the five-membered ring in the sabinene molecule, while (-)-sabina ketone was produced as a minor product. An uncommon mechanistic route was suggested and supported by density functions theory (DFT), which could suitably explain the formation of these ketones. DFT results supported a proposed concerted mechanism for the Csingle bondC activation, like a semipinacol rearrangement, which includes a heterolysis of the Pd-C bond and synchronous cleavage of the Csingle bondC bond in an intermediate organopalladium peroxo complex. We highly believe that such findings allow a step forward a deep understanding of such organic transformation, helping in future new routes for value-added products. | pt_BR |
dc.identifier.citation | VIEIRA, C. G. et al. Palladium-catalyzed sabinene oxidation with hydrogen peroxide: smart fragrance production and DFT insights. Molecular Catalysis, v. 517, artigo 112033, 2022. Disponível em: <https://www.sciencedirect.com/science/article/pii/S2468823121006490>. Acesso em: 11 out. 2022. | pt_BR |
dc.identifier.doi | https://doi.org/10.1016/j.mcat.2021.112033 | pt_BR |
dc.identifier.issn | 2468-8231 | |
dc.identifier.uri | http://www.repositorio.ufop.br/jspui/handle/123456789/16589 | |
dc.identifier.uri2 | https://www.sciencedirect.com/science/article/pii/S2468823121006490 | pt_BR |
dc.language.iso | en_US | pt_BR |
dc.rights | restrito | pt_BR |
dc.subject | Density functions theory study | pt_BR |
dc.title | Palladium-catalyzed sabinene oxidation with hydrogen peroxide : smart fragrance production and DFT insights. | pt_BR |
dc.type | Artigo publicado em periodico | pt_BR |
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