Hydroformylation and one-pot hydroformylation/epoxy ring cleavage of limonene oxide: A sustainable access to biomass-based multi-functional fragrances

Oliveira, Mileny P. de; Delolo, Fábio G.; Avendaño-Villarreal, Jesus A.; Santos, Eduardo N. dos; Gusevskaya, Elena V.

doi:10.1016/j.apcata.2021.118082

Cited by 5 publications

(4 citation statements)

References 30 publications

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“…In the past decade, Gusevskaya and coworkers developed a series of catalytic transformations of renewable alkenes to gain access to new fragrant molecules [ 30 , 131 , 132 , 133 , 134 , 135 , 136 , 137 , 138 ]. For example, they subjected myrtenol and nopol to the synthesis of polycyclic fragrances via hydroformylation and the subsequent intramolecular acetalization [ 131 ].…”

Section: Synthesis Of Heterocyclic Fragrances Via Addition-type React...mentioning

confidence: 99%

Synthesis of Cyclic Fragrances via Transformations of Alkenes, Alkynes and Enynes: Strategies and Recent Progress

Lin¹,

Huang²,

Ouyang³

et al. 2022

Molecules

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With increasing demand for customized commodities and the greater insight and understanding of olfaction, the synthesis of fragrances with diverse structures and odor characters has become a core task. Recent progress in organic synthesis and catalysis enables the rapid construction of carbocycles and heterocycles from readily available unsaturated molecular building blocks, with increased selectivity, atom economy, sustainability and product diversity. In this review, synthetic methods for creating cyclic fragrances, including both natural and synthetic ones, will be discussed, with a focus on the key transformations of alkenes, alkynes, dienes and enynes. Several strategies will be discussed, including cycloaddition, catalytic cyclization, ring-closing metathesis, intramolecular addition, and rearrangement reactions. Representative examples and the featured olfactory investigations will be highlighted, along with some perspectives on future developments in this area.

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Section: Synthesis Of Heterocyclic Fragrances Via Addition-type React...mentioning

confidence: 99%

Synthesis of Cyclic Fragrances via Transformations of Alkenes, Alkynes and Enynes: Strategies and Recent Progress

Lin¹,

Huang²,

Ouyang³

et al. 2022

Molecules

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“…Limonene has found practical application in biorefineries, where post-production waste generated during the production of, e.g., orange juices, is processed into commercially useful compounds and constitutes a suitable raw material for the production of important products used in the flavor and fragrance industry [16] in the textile industry for the production of fibers [17] or in pharmacy/medicine [18,19]. However, limonene oxidation products are much more valuable than the substrate from which they are obtained and play an important role as an ingredient for the synthesis of fragrances or drugs [20,21], in the production of biodegradable polymers [22][23][24][25][26], or as a solvent/reactive diluent in the production of epoxy resins [26]. The main products of the C 10 H 16 oxidation reactions are demonstrated in Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

DFT Studies of the Activity and Reactivity of Limonene in Comparison with Selected Monoterpenes

Rydel-Ciszek

2024

Molecules

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Nowadays, the effective processing of natural monoterpenes that constitute renewable biomass found in post-production waste into products that are starting materials for the synthesis of valuable compounds is a way to ensure independence from non-renewable fossil fuels and can contribute to reducing global carbon dioxide emissions. The presented research aims to determine, based on DFT calculations, the activity and reactivity of limonene, an organic substrate used in previous preparative analyses, in comparison to selected monoterpenes such as cymene, pinene, thymol, and menthol. The influence of the solvent model was also checked, and the bonds most susceptible to reaction were determined in the examined compounds. With regard to EHOMO, it was found that limonene reacts more easily than cymene or menthol but with more difficultly than thymol and pienene. The analysis of the global chemical reactivity descriptors “locates” the reactivity of limonene in the middle of the studied monoterpenes. It was observed that, among the tested compounds, the most reactive compound is thymol, while the least reactive is menthol. The demonstrated results can be a reference point for experimental work carried out using the discussed compounds, to focus research on those with the highest reactivity.

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“…[26,27] For several years we have been focusing our efforts on the catalytic valorization of natural compounds; [28,29] in particular, through the hydroformylation-based tandem processes. [30][31][32][33][34][35][36][37] In the present work, we describe the HAM reaction of a series of allylic and homoallylic terpenic alcohols with secondary amines aiming to obtain complex amines of pharmaceutical relevance. The hydroformylation of allylic and homoallylic alcohols usually results directly in cyclic hemiacetals due to the fast cyclization of primarily formed hydroxyaldehydes, [38] which could present an obstacle for the HAM sequence.…”

Section: Introductionmentioning

confidence: 99%

“…For several years we have been focusing our efforts on the catalytic valorization of natural compounds; [28,29] in particular, through the hydroformylation‐based tandem processes [30–37] . In the present work, we describe the HAM reaction of a series of allylic and homoallylic terpenic alcohols with secondary amines aiming to obtain complex amines of pharmaceutical relevance.…”

Section: Introductionmentioning

confidence: 99%

Hydroaminomethylation of Natural Allylic and Homoallylic Alcohols: A Ligand‐Controlled Route to New Amines

et al. 2022

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Hydroaminomethylation (HAM) is a tandem catalytic process that allows accessing amines from olefin scaffolds and is perfectly aligned with green chemistry precepts. In this work, HAM was applied to the natural hydroxyolefins: isoprenol, linalool, nerolidol, and isopulegol. Employing 4‐methylpiperidine, morpholine, and 1,2,3,4‐tetrahydroisoquinoline as counterparts, several new, structurally complex amines were prepared from biorenewable, low‐cost substrates, opening a path to exploit this structure diversity in biological activity. By the appropriate choice of rhodium‐based catalytic systems, as well as the reaction conditions, the necessary fine tuning for each counterpart was achieved. The unpromoted rhodium system leaded mostly to aminoalcohols, while certain phosphorus(III)‐promoted rhodium systems afforded amines containing a tetrahydropyran or a tetrahydrofuran moiety in moderate to high yields.

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Hydroformylation and one-pot hydroformylation/epoxy ring cleavage of limonene oxide: A sustainable access to biomass-based multi-functional fragrances

Cited by 5 publications

References 30 publications

Synthesis of Cyclic Fragrances via Transformations of Alkenes, Alkynes and Enynes: Strategies and Recent Progress

Synthesis of Cyclic Fragrances via Transformations of Alkenes, Alkynes and Enynes: Strategies and Recent Progress

DFT Studies of the Activity and Reactivity of Limonene in Comparison with Selected Monoterpenes

Hydroaminomethylation of Natural Allylic and Homoallylic Alcohols: A Ligand‐Controlled Route to New Amines

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