Electro-mediated PhotoRedox Catalysis for Selective C(sp(3))-O Cleavages of Phosphinated Alcohols to Carbanions

Tian, Xianhai; Karl, Tobias A.; Reiter, Sebastian; Yakubov, Shahboz; Vivie-Riedle, Regina de; König, Burkhard and Barham, Joshua P. (2021): Electro-mediated PhotoRedox Catalysis for Selective C(sp(3))-O Cleavages of Phosphinated Alcohols to Carbanions. In: Angewandte Chemie-International Edition, Vol. 60, No. 38: pp. 20817-20825

Abstract

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: Journal article
• Faculties: Chemistry and Pharmacy > Department of Chemistry
• Subjects: 500 Science > 540 Chemistry
• ISSN: 1433-7851
• Language: English