Berg, Nele and Bergwinkl, Sebastian and Nuernberger, Patrick and Horinek, Dominik and Gschwind, Ruth M. (2021) Extended Hydrogen Bond Networks for Effective Proton-Coupled Electron Transfer (PCET) Reactions: The Unexpected Role of Thiophenol and Its Acidic Channel in Photocatalytic Hydroamidations. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 143 (2). pp. 724-735. ISSN 0002-7863, 1520-5126
Full text not available from this repository. (Request a copy)Abstract
Preorganization and aggregation in photoredox catalysis can significantly affect reactivities or selectivities but are often neglected in synthetic and mechanistic studies, since the averaging effect of flexible ensembles can effectively hide the key activation signatures. In addition, aggregation effects are often overlooked due to highly diluted samples used in many UV studies. One prominent example is Knowles's acceleration effect of thiophenol in proton-coupled electron transfer mediated hydroamidations, for which mainly radical properties were discussed. Here, cooperative reactivity enhancements of thiophenol/disulfide mixtures reveal the importance of H-bond networks. For the first time an in-depth NMR spectroscopic aggregation and H-bond analysis of donor and acceptor combined with MD simulations was performed revealing that thiophenol acts also as an acid. The formed phosphate-H+-phosphate dimers provide an extended H-bond network with amides allowing a productive regeneration of the photocatalyst to become effective. The radical and acidic properties of PhSH were substituted by Ph2S2 and phosphoric acid. This provides a handle for optimization of radical and ionic channels and yields accelerations up to 1 order of magnitude under synthetic conditions. Reaction profiles with different light intensities unveil photogenerated amidyl radical reservoirs lasting over minutes, substantiating the positive effect of the H-bond network prior to radical cyclization. We expect the presented concepts of effective activation via H-bond networks and the reactivity improvement via the separation of ionic and radical channels to be generally applicable in photoredox catalysis. In addition, this study shows that control of aggregates and ensembles will be a key to future photocatalysis.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ANTI-MARKOVNIKOV HYDROAMINATION; MODEL; ALKENES; PHENOXYL/PHENOL; BENZYL/TOLUENE; OXIDATION; MECHANISM; SYSTEMS; PHENOLS; ACCESS |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry VI - Physical Chemistry (Solution Chemistry) > Prof. Dr. Dominik Horinek Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Physical Chemistry I > Prof. Dr. Patrick Nürnberger |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 17 Aug 2022 05:16 |
| Last Modified: | 17 Aug 2022 05:16 |
| URI: | https://pred.uni-regensburg.de/id/eprint/45748 |
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