Ruthenium‐Catalyzed Cross Metathesis of β‐Myrcene and its Derivatives with Methyl Acrylate

Behr, Arno; Johnen, Leif; Wintzer, Andreas; Çetin, Arzu Gümüş; Neubert, Peter; Domke, Lutz

doi:10.1002/cctc.201500993

Cited by 9 publications

(5 citation statements)

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“…[27] We have also established ar oute to produce octyl methoxycinnamate, am ajor UV-A filter used in sunscreen lotions, through the Rucatalyzed cross-metathesis of the naturallyo ccurring anethole with the commodity chemical 2-ethylhexyl acrylate. [12,28,[31][32][33] In this work we comparedt he performance of traditional solvents as well as other solvents regarded as greener alternatives with p-cymene in the challenging cross-metathesis of naturally occurring propenylbenzenes with acrylates,a sw ell as other substrates. [12,28,[31][32][33] In this work we comparedt he performance of traditional solvents as well as other solvents regarded as greener alternatives with p-cymene in the challenging cross-metathesis of naturally occurring propenylbenzenes with acrylates,a sw ell as other substrates.…”

Section: Introductionmentioning

confidence: 99%

“…[28] More generally, the cross-metathesis of natural products with acrylates is an excellent approachf or the synthesis of monomers, polymers, [29,30] or fine chemicals. [12,28,[31][32][33] In this work we comparedt he performance of traditional solvents as well as other solvents regarded as greener alternatives with p-cymene in the challenging cross-metathesis of naturally occurring propenylbenzenes with acrylates,a sw ell as other substrates.…”

Section: Introductionmentioning

confidence: 99%

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p‐Cymene as Solvent for Olefin Metathesis: Matching Efficiency and Sustainability

Granato

Santos

2017

ChemSusChem

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The underexploited biorenewable p-cymene is employed as a solvent for the metathesis of various substrates. p-Cymene is a nontoxic compound that can be obtained in large amounts as a side product of the cellulose and citrus industry. For the cross-metathesis of estragole with methyl acrylate, this solvent prevents the consecutive double-bond isomerization of the product and affords the best yield of all solvents tested. Undesired consecutive isomerization is a major challenge for many substrates in olefin metathesis, including pharmaceutical precursors, and the use of p-cymene as a solvent may be a way to prevent it. This solvent results in a better metathesis performance than toluene for the three substrates tested in this work, matching its performance for two other substrates.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

p‐Cymene as Solvent for Olefin Metathesis: Matching Efficiency and Sustainability

Granato

Santos

2017

ChemSusChem

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“…attracted attention as a high potential feedstock for fine chemical synthesis using transition metal catalysis. [7,8,9,10] We previously reported a thermochemical route (Scheme 1) to 1,3-butadiene, 1,3-pentadiene, and isoprene from the vapor-phase dehydradecyclization of biomass-derived saturated fivemembered cyclic ethers tetrahydrofuran (THF), 2methyltetrahydrofuran (2-MTHF), and 3methyltetrahydrofuran (3-MTHF), respectively. [11,12] These studies reported high selectivity to corresponding dienes on phosphoruscontaining all-silica zeolites.…”

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confidence: 99%

Dehydra-Decyclization of 2-Methyltetrahydrofuran to Pentadienes on Boron-Containing Zeolites

Kumar¹,

Liu²,

Xu³

et al. 2020

Preprint

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Biomass-derived 2-methyltetrahydrofuran (2-MTHF) undergoes tandem ring-opening and dehydration (dehydra-decyclization) to linear pentadienes, namely 1,3-pentadiene and 1,4-pentadiene. It can also fragment to butenes and formaldehyde through a competing retro-Prins condensation pathway. Using detailed kinetic measurements of 2-MTHF dehydra-decyclization on zeolites with disparate acidities (boro- and alumino-silicates) and micropore environments (MFI, MWW, and BEA), weakly acidic borosilicates were shown to exhibit ca. 10-30% higher selectivity to dienes at about five-to-sixty times lower proton-normalized rates than aluminosilicates (453-573 K). Dehydra-decyclization site time yields (STYs) were invariant for aluminosilicates within the investigated frameworks, indicating the absence of pore-confinement influence. However, individual site-normalized reaction rates varied by almost an order of magnitude on borosilicates in the order MWW > MFI > BEA at a given temperature (523 K), indicating the different nature of active sites in these weak solid acids. The diene distribution remained far from equilibrium and was tuned towards the desirable conjugated diene (1,3-pentadiene) by facile isomerization of 1,4-pentadiene. This tuning capability was facilitated by high bed residence times, as well as the smaller micropore sizes among the considered zeolite frameworks. The suppression of competing pathways and promotion of 1,4-pentadiene isomerization events lead to a hitherto unreported ∼86% 1,3-pentadiene yield and an overall ∼ 89% combined linear C5 dienes’ yield at near quantitative (~98%) 2-MTHF conversion on the borosilicate B-MWW, without a significant reduction in diene selectivities for at least 80 hours time-on-stream under low space velocity (0.85 g reactant/g cat./h) and high temperature (658 K) conditions. Finally, starting with iso-conversion levels (ca. 21-26%) and using total turnover numbers (TONs) accrued over the entire catalyst lifetime as the stability criterion, borosilicates were demonstrated to be significantly more stable than aluminosilicates under reaction conditions (~3-6x higher TONs).

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“…Besides the hydroamination and hydroaminomethylation, a couple of homogeneously catalyzed reactions of β ‐myrcene were developed in our group resulting in esters of different chain length with specialized applications, for instance, in flavors and fragrances. Branched C11‐esters were obtained in 61 % yields by palladium catalyzed methoxycarbonylation, as well as by ruthenium catalyzed cross metathesis with methyl acrylate . However, ruthenium catalyzed codimerization with methyl acrylate yields different C13‐esters (Figure ) …”

Section: C6 Molecules (Renewables)mentioning

confidence: 99%

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

et al. 2018

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For many years, the efficient use of resources has been a major and permanent challenge for the chemical industry. The implementation of alternative resources such as renewables and carbon dioxide has been a subject of considerable discussion, but also the more efficient use of long known bulk chemicals is of great interest. Among them, 1,3‐dienes such as 1,3‐butadiene from the C4 cut of the naphtha cracker as well as isoprene, piperylene and cyclopentadiene from the corresponding C5 section are important substrates. These dienes are presently employed in various markets, with the greatest importance being in the production of polymers and copolymers. However, homogeneous transition metal catalysis has proven to be a versatile tool to functionalize these important 1,3‐dienes to low molecular weight fine chemicals by introducing, for example, nitrogen, oxygen or silicon. Hence, an upgraded use of the corresponding products as agrochemicals, pharmaceuticals, fragrances or special detergents is close at hand. The main approaches in the topic of homogeneous functionalization reactions of the industrially relevant 1,3‐dienes will be summarized and discussed within the present article. Besides that, novel applications including renewable 1,3‐dienes, for example β‐myrcene and β‐farnesene, as well as the application of CO2 in telomerization, will be critically discussed.

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Ruthenium‐Catalyzed Cross Metathesis of β‐Myrcene and its Derivatives with Methyl Acrylate

Cited by 9 publications

References 61 publications

p‐Cymene as Solvent for Olefin Metathesis: Matching Efficiency and Sustainability

p‐Cymene as Solvent for Olefin Metathesis: Matching Efficiency and Sustainability

Dehydra-Decyclization of 2-Methyltetrahydrofuran to Pentadienes on Boron-Containing Zeolites

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

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