Electric field–assisted anion-π catalysis on carbon nanotubes in electrochemical microfluidic devices

Gutiérrez López, M. Ángeles, Ali, Rojan, Tan, Mei-Ling, Sakai, Naomi, Wirth, Thomas ORCID: https://orcid.org/0000-0002-8990-0667 and Matile, Stefan 2023. Electric field–assisted anion-π catalysis on carbon nanotubes in electrochemical microfluidic devices. Science Advances 9 (41) , eadj5502. 10.1126/sciadv.adj5502

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Abstract

The vision to control the charges migrating during reactions with external electric fields is attractive because of the promise of general catalysis, emergent properties, and programmable devices. Here, we explore this idea with anion-π catalysis, that is the stabilization of anionic transition states on aromatic surfaces. Catalyst activation by polarization of the aromatic system is most effective. This polarization is induced by electric fields. The use of electrochemical microfluidic reactors to polarize multiwalled carbon nanotubes as anion-π catalysts emerges as essential. These reactors provide access to high fields at low enough voltage to prevent electron transfer, afford meaningful effective catalyst/substrate ratios, and avoid interference from additional electrolytes. Under these conditions, the rate of pyrene-interfaced epoxide-opening ether cyclizations is linearly voltage-dependent at positive voltages and negligible at negative voltages. While electromicrofluidics have been conceived for redox chemistry, our results indicate that their use for supramolecular organocatalysis has the potential to noncovalently electrify organic synthesis in the broadest sense.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	American Association for the Advancement of Science
ISSN:	2375-2548
Funders:	University of Geneva, the National Centre of Competence in Research (NCCR) Molecular Systems Engineering (51NF40-182895), and the Swiss NSF for financial support (Excellence Grant 200020 204175; Swiss-ERC Advanced Grant TIMEUP, TMAG-2_209190
Date of First Compliant Deposit:	21 November 2023
Date of Acceptance:	7 September 2023
Last Modified:	22 Nov 2023 11:30
URI:	https://orca.cardiff.ac.uk/id/eprint/164112

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