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

Porter, Tyler M.; Kanan, Matthew W.

doi:10.1039/D0SC04548A

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

Journal Article · Wed Nov 11 00:00:00 EST 2020 · Chemical Science

DOI:https://doi.org/10.1039/D0SC04548A· OSTI ID:1675014

Porter, Tyler M. ^[1];

^[1]

Department of Chemistry, Stanford University, Stanford, USA

C–H carboxylation is an attractive transformation for both streamlining synthesis and valorizing CO₂. The high bond strength and very low acidity of most C–H bonds, as well as the low reactivity of CO₂, present fundamental challenges for this chemistry. Conventional methods for carboxylation of electron-rich heteroarenes require very strong organic bases to effect C–H deprotonation. Here we show that alkali carbonates (M₂CO₃) dispersed in mesoporous TiO₂ supports (M₂CO₃/TiO₂) effect CO₃^2- promoted C–H carboxylation of thiophene- and indole-based heteroarenes in gas–solid reactions at 200–320 C. M₂CO₃/TiO₂ materials are strong bases in this temperature regime, which enables deprotonation of very weakly acidic bonds in these substrates to generate reactive carbanions. In addition, we show that M₂CO₃/TiO₂ enables C3 carboxylation of indole substrates via an apparent electrophilic aromatic substitution mechanism. No carboxylations take place when M₂CO₃/TiO₂ is replaced with un-supported M₂CO₃, demonstrating the critical role of carbonate dispersion and disruption of the M₂CO₃ lattice. After carboxylation, treatment of the support-bound carboxylate products with dimethyl carbonate affords isolable esters and the M₂CO₃/TiO₂ material can be regenerated upon heating under vacuum. Our results provide the basis for a closed cycle for the esterification of heteroarenes with CO₂ and dimethyl carbonate.

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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:: 1675014

Alternate ID(s):: OSTI ID: 1817112; OSTI ID: 1972325

Journal Information:: Chemical Science, Journal Name: Chemical Science Vol. 11 Journal Issue: 43; ISSN 2041-6520

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

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