Tian, Xianhai and Karl, Tobias A. and Reiter, Sebastian and Yakubov, Shahboz and de Vivie-Riedle, Regina and Koenig, Burkhard and Barham, Joshua P. (2021) Electro-mediated PhotoRedox Catalysis for Selective C(sp(3))-O Cleavages of Phosphinated Alcohols to Carbanions. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 60 (38). pp. 20817-20825. ISSN 1433-7851, 1521-3773
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We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage of C(sp(3))-O bonds of phosphinated alcohols to alkyl carbanions. As well as deoxygenations, olefinations are reported which are E-selective and can be made Z-selective in a tandem reduction/photosensitization process where both steps are photoelectrochemically promoted. Spectroscopy, computation, and catalyst structural variations reveal that our new naphthalene monoimide-type catalyst allows for an intimate dispersive precomplexation of its radical anion form with the phosphinate substrate, facilitating a reactivity-determining C(sp(3))-O cleavage. Surprisingly and in contrast to previously reported photoexcited radical anion chemistries, our conditions tolerate aryl chlorides/bromides and do not give rise to Birch-type reductions.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ARYL HALIDES; ORGANIC-SYNTHESIS; LIGHT; REDUCTION; BOND; ACTIVATION; COMPLEXES; CHAIN; ISOMERIZATION; TRANSITION; deoxygenation; olefination; photoelectrochemistry; preassembly; radical anion |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Lehrstuhl Prof. Dr. Burkhard König |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 10 Aug 2022 10:54 |
| Last Modified: | 10 Aug 2022 10:54 |
| URI: | https://pred.uni-regensburg.de/id/eprint/46428 |
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