Transition metal triflate catalyzed conversion of alcohols, ethers and esters to olefins

Keskiväli, Juha; Parviainen, Arno; Lagerblom, Kalle; Repo, Timo

doi:10.1039/c8ra02437e

Cited by 10 publications

(28 citation statements)

References 32 publications

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“…Transformation of higher ethers to olefins is still a challenge at present stage, which usually requires high temperature (ca. 450–650 °C) or with low yield (below 30%) 23,24 . Very interestingly, butene could be generated very efficiently at much lower temperature in our catalytic system.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of higher carboxylic acids from ethers, CO2 and H2

et al. 2019

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Synthesis of higher carboxylic acids using CO2 and H2 is of great importance, because CO2 is an attractive renewable C1 resource and H2 is a cheap and clean reductant. Herein we report a route to produce higher carboxylic acids via reaction of ethers with CO2 and H2. We show that the reaction can be efficiently catalyzed by an IrI4 catalyst with LiI as promoter at 170 °C, 5 MPa of CO2 and 2 MPa of H2. The catalytic system applies to various ether substrates. The mechanistic study indicates that the ethers are converted to olefins, which are further transformed into alkyl iodides. The higher carboxylic acids are produced by carbonylation of alkyl iodides with CO generated in situ via RWGS reaction. This report offers an alternative strategy of higher carboxylic acid synthesis and CO2 transformation.

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Section: Resultsmentioning

confidence: 99%

Synthesis of higher carboxylic acids from ethers, CO2 and H2

et al. 2019

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“…Tea tree oil consists primarily of terpineols, and its abundance offers a potential olefin source. 45 Thus, linalool and terpinen-4-ol were used as model substrates (Table 1, entries 8 and 9), and dehydration is found to occur under mild conditions to selectively form the desired products (see the Supporting Information for detailed product and yield data). 12,45,46 Next, a broader scope of alcohols was screened with AC/ MoO 2 to probe substrate tolerance and activity.…”

Section: ■ Introductionmentioning

confidence: 99%

Diverse Mechanistic Pathways in Single-Site Heterogeneous Catalysis: Alcohol Conversions Mediated by a High-Valent Carbon-Supported Molybdenum-Dioxo Catalyst

Das

et al. 2022

ACS Catal.

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With the increase in the importance of renewable resources, chemical research is shifting focus toward substituting petrochemicals with biomass-derived analogues and platform-molecule transformations such as alcohol processing. To these ends, in-depth mechanistic understanding is key to the rational design of catalytic systems with enhanced activity and selectivity. Here we discuss in detail the structure and reactivity of a single-site active carbon-supported molybdenum-dioxo catalyst (AC/MoO2) and the mechanism(s) by which it mediates alcohol dehydration. A range of tertiary, secondary, and primary alcohols as well as selected bio-based terpineols are investigated as substrates under mild reaction conditions. A combined experimental substituent effect/kinetic/kinetic isotope effect/EXAFS/DFT computational analysis indicates that (1) water assistance is a key element in the transition state; (2) the experimental kinetic isotopic effect and activation enthalpy are 2.5 and 24.4 kcal/mol, respectively, in good agreement with the DFT results; and (3) several computationally identified intermediates including Mo-oxo-hydroxy-alkoxide and cage-structured long-range water-coordinated Mo-dioxo species are supported by EXAFS. This structurally and mechanistically well-characterized single-site system not only effects efficient transformations but also provides insight into rational catalyst design for future biomass processes.

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“…Even though metal trifluoromethanesulfonates (triflates, − OTf) see wide applications as catalysts[ 1 , 2 ] or leaving groups in both organic[ 3 , 4 , 5 , 6 ] and inorganic chemistry,[ 7 , 8 , 9 ] their solid‐state chemistry has not seen much attention. Homoleptic triflates are crystallographically poorly investigated, even though these weakly coordinating anions (WCAs)[ 10 , 11 ] are, amongst others, widely used in organic reactions,[ 12 , 13 , 14 , 15 ] and have been proposed for novel applications such as the recycling of thoria in thorium‐based nuclear fuels. [16] There may be a variety of reasons for this, as triflates generally crystallise rather poorly, and they are readily displaced by stronger donors such as water.…”

Section: Introductionmentioning

confidence: 99%

Ammonium Pertechnetate in Mixtures of Trifluoromethanesulfonic Acid and Trifluoromethanesulfonic Anhydride

et al. 2021

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Ammonium pertechnetate reacts in mixtures of trifluoromethanesulfonic anhydride and trifluoromethanesulfonic acid under final formation of ammonium pentakis(trifluoromethanesulfonato)oxidotechnetate(V), (NH4)2[TcO(OTf)5]. The reaction proceeds only at exact concentrations and under the exclusion of air and moisture via pertechnetyl trifluoromethanesulfonate, [TcO3(OTf)], and intermediate TcVI species. 99Tc nuclear magnetic resonance (NMR) has been used to study the TcVII compound and electron paramagnetic resonance (EPR), 99Tc NMR and X‐ray absorption near‐edge structure (XANES) experiments indicate the presence of the reduced technetium species. In moist air, (NH4)2[TcO(OTf)5] slowly hydrolyses under formation of the tetrameric oxidotechnetate(V) (NH4)4[{TcO(TcO4)4}4] ⋅10 H2O. Single‐crystal X‐ray crystallography was used to determine the solid‐state structures. Additionally, UV/Vis absorption and IR spectra as well as quantum chemical calculations confirm the identity of the species.

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Transition metal triflate catalyzed conversion of alcohols, ethers and esters to olefins

Cited by 10 publications

References 32 publications

Synthesis of higher carboxylic acids from ethers, CO2 and H2

Synthesis of higher carboxylic acids from ethers, CO2 and H2

Diverse Mechanistic Pathways in Single-Site Heterogeneous Catalysis: Alcohol Conversions Mediated by a High-Valent Carbon-Supported Molybdenum-Dioxo Catalyst

Ammonium Pertechnetate in Mixtures of Trifluoromethanesulfonic Acid and Trifluoromethanesulfonic Anhydride

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