A Fluorogenic Substrate for Quinoline Reduction: Pnictogen‐Bonding Catalysis in Aqueous Systems

Article Article scientifique Article A Fluorogenic Substrate for Quinoline Reduction: Pnictogen‐Bonding Catalysis in Aqueous Systems eng 2024-03-29 2024-03-29 author Renno Giacomo Department of Organic Chemistry University of Geneva Quai Ernest Ansermet 30 1211 Geneva 4 Switzerland 403424 Département de chimie organique (CHIOR) author Zhang Xiao Qing Department of Organic Chemistry University of Geneva Quai Ernest Ansermet 30 1211 Geneva 4 Switzerland 632661 author Frontera Antonio Department of Chemistry Universitat de les Illes Balears Crta. de Valldemossa km 7.5 07122 Palma de Mallorca Baleares Spain author Sakai Naomi 0000-0002-9460-1944 Department of Organic Chemistry University of Geneva Quai Ernest Ansermet 30 1211 Geneva 4 Switzerland 131140 Département de chimie organique (CHIOR) author Matile Stefan 0000-0002-8537-8349 Department of Organic Chemistry University of Geneva Quai Ernest Ansermet 30 1211 Geneva 4 Switzerland 129654 Département de chimie organique (CHIOR) e202400015 10.1002/hlca.202400015 0018-019X https://onlinelibrary.wiley.com/doi/10.1002/hlca.202400015 <p>It is often said that pnictogen‐bonding catalysis, and σ ‐hole catalysis in general, would not work in aqueous systems because the solvent would interfere as an overcompetitive pnictogen‐bond acceptor. In this study, we show that the transfer of pnictogen‐bonding catalysis from hydrophobic solvents to aqueous systems is possible by replacing only hydrophobic with hydrophilic substrates, without changing catalyst or reaction. This differs from conventional covalent Lewis acid catalysts, which are instantaneously destroyed by ligand exchange. With their water‐proof substituents in place of exchangeable ligands, pnictogen‐bonding catalysts, the supramolecular counterpart of Lewis acid catalysts, are evinced to catalyze transfer hydrogenation of quinolines in neutral aqueous systems. To secure these results, we introduce a water‐soluble fluorogenic substrate that releases a coumarin upon the reduction of quinolines instead of activated quinolidiniums, and stiborane catalysts with deepened σ holes. They demonstrate that pnictogen‐bonding catalysts can operate in higher‐order architectures for supramolecular systems catalysis under biologically relevant conditions, and provide an operational assay for high‐throughput catalyst screening by fluorescence imaging, in situ under relevant aqueous conditions.</p> Dewey 540 Swiss National Science Foundation Synthetic Supramolecular Systems at Work 204175 CH Projects Swiss National Science Foundation NCCR MSE: Molecular Systems Engineering (phase III) 205608 CH Programmes Swiss National Science Foundation Translational Dynamic Covalent Exchange Cascades (TIMEUP) 209190 CH Programmes 36 Département de chimie organique 141 false 761 Groupe Matile Helvetica chimica acta 107 5 96cf67fc-83a8-40d5-9af8-4a4002ecd333 Article (Published version) Public file.pdf 11753802 application/pdf CC BY-4.0 05ceb1fb07f5b9562b60cb3f3bfd979f4467526aa0966cf614a6e6e74dce445c openAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie organique

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A Fluorogenic Substrate for Quinoline Reduction: Pnictogen‐Bonding Catalysis in Aqueous Systems	Helvetica chimica acta			2024	110	57

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Zhang, Xiao Qing