Synthesis of potential bisphenol A substitutes by isomerising metathesis of renewable raw materials

Trita, Andrada Stefania; Over, Lena Charlotte; Pollini, Jacqueline; Baader, Sabrina; Riegsinger, Sven; Meier, Michael A. R.; Gooßen, Lukas J.

doi:10.1039/c7gc00553a

Cited by 84 publications

(47 citation statements)

References 60 publications

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“…22 Its evenly rising boiling point curve fulfils the strict specifications prescribed by the fuel standard EN 590 for modern (petrol) diesel engines. The [Pd I (µ-Br) t Bu 3 P] 2 isomerization catalyst at the basis of these recent developments in equilibrium isomerizing metathesis [18][19][20][21][22] was first reported by Mingos, 23 Prashad, 24 and Hartwig, 25 who first utilized the Pd I dimer as precatalyst in Pd 0promoted cross-couplings. They found it to be an excellent catalyst for couplings of aryl chlorides and bromides e.g.…”

Section: Introductionmentioning

confidence: 99%

Dinuclear Pd^I Catalysts in Equilibrium Isomerizations: Mechanistic Understanding, in Silico Casting, and Catalyst Development

Sivendran

Maity

et al. 2020

ACS Catal.

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The unique reactivity profile of the dinuclear Pd I complex [Pd I (µ-Br) t Bu 3 P] 2 as an isomerization co-catalyst has enabled orthogonal tandem processes ranging from styrene syntheses to biodiesel refining. We have now elucidated the mechanistic basis of its distinct catalytic profile by DFT calculations and experimental studies. Activation of the catalyst proceeds intramolecularly, giving rise to a dinuclear complex composed of a reactive palladium hydride and an inert palladacycle. This complex mediates double-bond migrations with an energy span of 9.5 kcal/mol, which is well below those calculated for known catalysts. Its dissociation leads to an even more active monophosphinopalladium hydride catalyst and an inert dinuclear bispalladacycle. In the main deactivation pathway, two mononuclear Pd species react with each other, liberating a hydrogenation product and regenerating the catalyst precursor [Pd I (µ-Br) t Bu 3 P] 2. The experimentally observed build-up of dinuclear palladacycles during the catalysis is, thus, the result of a conversion of binuclear into mononuclear Pd-H catalyst. Phosphines, which would deactivate metathesis cocatalysts, are not liberated at any stage. This explains the unique suitability of [Pd I (µ-Br) t Bu 3 P] 2 for isomerizing metatheses. The mechanistic insights were used for the in silico casting of a catalyst generation, targeting complexes with a reduced barrier towards the formation of dinuclear Pd-H species, a low energy span of the catalytic cycles, and increased barriers either towards deactivation or, alternatively, towards dissociation to short-lived mononuclear complexes. Complexes with bisadamantyl-n-butylphosphine ligands were identified as lead structures. Experimental studies with model catalysts confirmed the validity of the predicted structureactivity relationship. SUPPORTING INFORMATION The Supporting Information is available free of charge on the ACS Publications website at DOI: xx.xxxx/jacs.xxxxxxx. Further mechanistic routes and energy profiles Full experimental and computational details

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Section: Introductionmentioning

confidence: 99%

Dinuclear Pd^I Catalysts in Equilibrium Isomerizations: Mechanistic Understanding, in Silico Casting, and Catalyst Development

Sivendran

Maity

et al. 2020

ACS Catal.

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“…[54] However, the cross metathesis of terminal olefins with methyl (2Z,4E)-hexadienoate (77) has been shown to selectively involve its 4,5 double bond leading to the formal introduction of a new substituent at C5. When equimolar amounts of (2) and (77), (78) or (79) were treated in dichloromethane at 40°C for 8 h in the presence of 5 mol% of Ru2, the new dienes (80)- (82) were produced in about 70 % yield as pure stereoisomers together with small amounts of the selfmetathesis product of (2) (Scheme 20). [55]…”

Section: Cross Metathesis With Functional Vinylic Partnersmentioning

confidence: 99%

“…In addition a subsequent hydrogenation under 10 bar of hydrogen in the presence of palladium on charcoal led to an overall yield of the (104) in 80 % yield (Scheme 30). [78] When ethylene was introduced as a cross metathesis partner, the ethenolysis [79] of the 2-propenyl intermediate took place leading to the formation of the desired styrenes (105) from eugenol, estragole, safrole, methyl eugenol in more than 85 % yield. [80] Whereas the cross metathesis of the vinylboronate (68) with allyl-substituted aromatics in the presence of the first generation Ru1 catalyst selectively led to alkenylboronates (Scheme 19) [53] the introduction of the bis-(2,6-diisopropylphenyl)imidazolinylidene ligand (SIPr) in the second generation Hoveyda type catalyst Ru18 changed the course of the reaction leading to the selective formation of β-styrylboronates resulting from an isomerization/cross metathesis sequence (Scheme 31).…”

Section: Isomerization and Cross Metathesismentioning

confidence: 99%

Transformations of bio‐sourced 4‐hydroxyphenylpropanoids based on olefin metathesis

et al. 2020

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4-Hydroxyphenylpropanoids represent an important class of natural products directly extracted from plants or derived from lignocelullosic materials. They are phenol derivatives equipped with a terminal propenyl group, which is perfectly suited for applications involving olefin metathesis processes. In this review, we show that conditions have been found to achieve their self-metathesis, cross metathesis as well as some sequential transformations with metathesis as a key step with high yields and controlled stereoselectivities. Some applications in multi-step synthesis of biological relevant natural products involving metathetic transformations of 4-hydroxyphenylpropanoids are also reported.

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“…For example, it has been converted to epoxy resins, displaying good properties. Furthermore, it is also used as a starting material for the preparation of polycarbonate, benzoxazine, and unsaturated resin . Because eugenol can be abundantly extracted from clove oil, cinnamon bark and leaves, tulsi leaves, and nutmeg, further extending the application of this compound is very necessary.…”

Section: Introductionmentioning

confidence: 99%

A Bio‐Based Allylphenol (Eugenol)‐Functionalized Fluorinated Maleimide with Low Dielectric Constant and Low Water Uptake

Fang

Zhou

Wang

et al. 2018

Macro Chemistry & Physics

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A bio‐based allylphenol (eugenol)‐functionalized fluoro‐containing maleimide derived from easily available cyanuric chloride is synthesized, and it is thermally transformed to a cross‐linked polymer. It is found that the polymer displays a 5% weight loss temperature of up to 413 °C, a glass transition temperature (T g) of up to 274 °C, and a thermal expansion coefficient (CTE) of 66.21 ppm °C−1 varying from 50 to 300 °C. The polymer is also found to exhibit lower water uptake (1.06%) than commercial 4,4′‐bismaleimidodiphenylmethane (BMI) resins (3%) and allyl‐modified bismaleimides (4.5%). This polymer is also found to indicate good dielectric properties with a dielectric constant (D k) of below 2.9 and a dissipation factor (D f) of less than 7 × 10−3 for frequencies varying from 40 Hz to 25 MHz. It is reported that, compared to the commercial BMI with CTE of 77.85 ppm °C−1 and D k of 3.50, this eugenol‐functionalized fluoro‐containing maleimide possesses good properties, suggesting that this new maleimide has potential application in the microelectronic industry.

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Synthesis of potential bisphenol A substitutes by isomerising metathesis of renewable raw materials

Abstract: Plant-derived alkenyl arenes were converted into polymer building blocks with low estrogenic activity via isomerising metathesis.

Cited by 84 publications

References 60 publications

Dinuclear Pd^I Catalysts in Equilibrium Isomerizations: Mechanistic Understanding, in Silico Casting, and Catalyst Development

Dinuclear Pd^I Catalysts in Equilibrium Isomerizations: Mechanistic Understanding, in Silico Casting, and Catalyst Development

Transformations of bio‐sourced 4‐hydroxyphenylpropanoids based on olefin metathesis

A Bio‐Based Allylphenol (Eugenol)‐Functionalized Fluorinated Maleimide with Low Dielectric Constant and Low Water Uptake

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Synthesis of potential bisphenol A substitutes by isomerising metathesis of renewable raw materials

Abstract: Plant-derived alkenyl arenes were converted into polymer building blocks with low estrogenic activity via isomerising metathesis.

Cited by 84 publications

References 60 publications

Dinuclear PdI Catalysts in Equilibrium Isomerizations: Mechanistic Understanding, in Silico Casting, and Catalyst Development

Dinuclear PdI Catalysts in Equilibrium Isomerizations: Mechanistic Understanding, in Silico Casting, and Catalyst Development

Transformations of bio‐sourced 4‐hydroxyphenylpropanoids based on olefin metathesis

A Bio‐Based Allylphenol (Eugenol)‐Functionalized Fluorinated Maleimide with Low Dielectric Constant and Low Water Uptake

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Product

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Dinuclear Pd^I Catalysts in Equilibrium Isomerizations: Mechanistic Understanding, in Silico Casting, and Catalyst Development

Dinuclear Pd^I Catalysts in Equilibrium Isomerizations: Mechanistic Understanding, in Silico Casting, and Catalyst Development