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

Article Article scientifique Article Electric field–assisted anion-π catalysis on carbon nanotubes in electrochemical microfluidic devices eng 2023-10-13 author Gutiérrez López M. Ángeles 0009-0007-4606-8392 Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, CH-1211 Geneva 4, Switzerland. author Ali Rojan 0009-0001-3861-0045 School of Chemistry, Cardiff University, Park Place, Main Building, Cardiff CF10 3AT, UK. author Tan Mei-Ling 0000-0001-7983-3432 Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, CH-1211 Geneva 4, Switzerland. author Sakai Naomi 0000-0002-9460-1944 Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, CH-1211 Geneva 4, Switzerland. 131140 Département de chimie organique (CHIOR) author Wirth Sandro Thomas 0000-0002-8990-0667 School of Chemistry, Cardiff University, Park Place, Main Building, Cardiff CF10 3AT, UK. 859265 author Matile Stefan 0000-0002-8537-8349 Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, CH-1211 Geneva 4, Switzerland. 129654 Département de chimie organique (CHIOR) eadj5502 10.1126/sciadv.adj5502 2375-2548 https://www.science.org/doi/10.1126/sciadv.adj5502 <p>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.</p> Dewey 540 36 Département de chimie organique 141 false 761 Groupe Matile Science advances 9 41 1eb01652-abfb-4d41-9fe8-e74528cae2e2 Article (Published version) Public sciadv.adj5502.pdf 1081951 application/pdf CC BY-4.0 b5e366fb36138ea0134d65adcc911b94d7cb3e1510981028b35e62fe8b8fc828 Vignette Public sciadv.adj5502-f1.jpg 162700 image/png openAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie organique

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Electric field–assisted anion-π catalysis on carbon nanotubes in electrochemical microfluidic devices	Science advances			2023	108	318

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Wirth, Sandro Thomas