A closed cycle for esterifying aromatic hydrocarbons with CO2 and alcohol

Xiao, Dianne J.; Chant, Emma D.; Frankhouser, Amy; Chen, Ying; Yau, Allison; Washton, Nancy M.; Kanan, Matthew W.

doi:10.1038/s41557-019-0313-y

Cited by 36 publications

(34 citation statements)

References 39 publications

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“…In addition, previous studies of benzothiophene substitution with strong electrophiles have shown selective substitution at C3, indicating that this is the preferred position for EAS reactivity. 39,44,45 The KIE values for benzothiophene are similar to what we have previously observed for benzene C-H carboxylation using the same M 2 CO 3 /TiO 2 materials, 34 as well as solid base-catalyzed reactions that feature ratedetermining deprotonation. 46 In contrast to benzothiophene, a KIE value of 1.1 was observed for C3 carboxylation of 1-methylindole, which is within NMR quantication error of 1.0.…”

Section: Kinetic Isotope Effects and Dft Calculations To Probe C-h Carboxylation Mechanismsupporting

confidence: 75%

“…4). 34 KIE values of 2.0 and 1.7 were observed for C2 carboxylation of benzothiophene using K 2 CO 3 /TiO 2 and Cs 2 CO 3 /TiO 2 , respectively. These values are consistent with a mechanism in which C-H deprotonation is slow and the resulting carbanion reacts rapidly with CO 2 (Scheme 2) and does not support an EAS mechanism.…”

Section: Kinetic Isotope Effects and Dft Calculations To Probe C-h Carboxylation Mechanismmentioning

confidence: 94%

“…1a) promotes the carboxylation of benzene and other aromatic hydrocarbon C-H bonds in gas-solid reactions (Scheme 1b). 34 Dispersion in mesopores disrupts the bulk M 2 CO 3 crystal structure, creating an amorphous material that can attain superbase reactivity, even in the presence of CO 2 . This carbonate-promoted C-H carboxylation of aromatic hydrocarbons takes place at moderate pressures and temperatures of $400 C. In this study, we begin to assess the generality and selectivity of this strategy using electron-rich heteroarenes, which have somewhat more acidic C-H bonds.…”

Section: Introductionmentioning

confidence: 99%

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Carbonate-promoted C–H carboxylation of electron-rich heteroarenes

Porter

Kanan

2020

Chem. Sci.

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Section: Kinetic Isotope Effects and Dft Calculations To Probe C-h Carboxylation Mechanismsupporting

confidence: 75%

Section: Kinetic Isotope Effects and Dft Calculations To Probe C-h Carboxylation Mechanismmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

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Carbonate-promoted C–H carboxylation of electron-rich heteroarenes

Porter

Kanan

2020

Chem. Sci.

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“…Biomass-derived bio-oil containing lignin-derived aromatic hydrocarbons is potential alternatives to fossil feedstocks in chemical production [1][2][3][4][5] . Unlocking this potential will bene t from progress in the selective hydrogenation of lignin-derived aromatic monomers to oxygen-functionalized chemical motifs -buildingblocks of pharmaceuticals, natural products, and agricultural chemicals -under gentle conditions, such as in scalable systems functioning at or near ambient pressures and at modest temperatures [6][7][8][9][10] .…”

Section: Introductionmentioning

confidence: 99%

Selective electrocatalytic hydrogenation of bio-oil to oxygenated chemicals via suppression of deoxygenation

Peng

Zhuang

et al. 2021

Preprint

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Catalytic hydrogenation of bio-oil provides an avenue to produce renewable chemicals. To this end, electrocatalytic hydrogenation is especially interesting when powered using low-carbon electricity; however, it has to date lacked the needed selectivity: when hydrogenating bio-oil to oxygenated hydrocarbons, for example, it reduces the desired oxygenated groups (-OH and -OCH3). Here we report that Rh and Au modulate electronic structure of Pt and steer intermediate energetics to favor the hydrogenation while suppressing deoxygenation using computational studies and in-situ spectroscopies. PtRhAu catalysts achieve a record 47% faradaic efficiency (FE) and a partial current density (Jp) of 28 mA·cm-2 toward oxygenated 2-methoxycyclohexanol from lignin-derived guaiacol under room temperature and ambient pressure, representing 1.5x FE and 3.5x Jp increases compared to the best prior reports. We further demonstrate an integrated lignin biorefinery where wood-derived lignin oils are selectively hydrogenated and funneled to the oxygenated 2-methoxy-4-propylcyclohexanol using PtRhAu catalysts.

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“…17 We recently reported that carbonate can promote the carboxylation of very weakly acidic C-H bonds in solvent-free alkali salts at intermediate temperatures under CO 2 . 18,19 Carbonate-promoted C-H carboxylation can be used to convert furan-2-carboxylate (furoate) into furan-2,5-dicarboxylate in high yield ( Fig. 2a), which has opened up a streamlined route from furfural to furan-2,5-dicarboxylic acid (FDCA).…”

mentioning

confidence: 99%