Improving Carbonate-Promoted C–H Carboxylation Using Mesoporous Carbon Supports

Chant, Emma D.; Li, Chastity S.; Kanan, Matthew W.

doi:10.1021/acssuschemeng.2c06977

Title: Improving Carbonate-Promoted C–H Carboxylation Using Mesoporous Carbon Supports

Journal Article · Mon Apr 03 00:00:00 EDT 2023 · ACS Sustainable Chemistry & Engineering

DOI:https://doi.org/10.1021/acssuschemeng.2c06977· OSTI ID:1972326

Chant, Emma D. ^[1];

^[1];

^[1]

Stanford Univ., CA (United States)

C–H carboxylation is an attractive way to utilize CO₂ for chemical production provided that it does not consume resource-intensive reagents. Alkali carbonates dispersed into the pores of mesoporous supports display strongly basic reactivity under CO₂, allowing them to be used as base promoters for C–H carboxylation of (hetero)arenes in the absence of other reagents or catalysts. Mesoporous oxides are convenient support materials, but only a relatively small fraction of the dispersed carbonate (ca. 10-20%) is converted to carboxylate products when metal oxide supports are used. Here we compare mesoporous oxide and carbon supports and investigate the dependence of carbonate reactivity on pore structure. We show that using mesoporous carbons supports can increase the carbonate conversion by 2–4x when compared to oxide supports. This improved carbonate reactivity is maintained across a variety of mesoporous carbons with different pore structures (ordered vs. disordered) and pore diameters, indicating that the dispersed carbonate is intrinsically more reactive on the surface of a carbon material compared to an oxide surface. Reaction of the carboxylate products with dimethyl carbonate yields isolable methyl esters as the final product and regenerates the dispersed carbonate. We show that mesoporous carbon supports are robust to at least 5 cycles of successive C–H carboxylation and methylation with dimethyl carbonate. Furthermore, understanding how the support structure affects dispersed carbonate reactivity is valuable for advancing C–H carboxylation toward practical application and utilizing these materials in other CO₂ transformations.

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Research Organization:: Stanford Univ., CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0020394

OSTI ID:: 1972326

Journal Information:: ACS Sustainable Chemistry & Engineering, Vol. 11, Issue 15; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
C−H functionalization
CO2 activation
solid base
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mesoporous carbons
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Title: Improving Carbonate-Promoted C–H Carboxylation Using Mesoporous Carbon Supports

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