Unknown

Dataset Information

0

Electro-mediated PhotoRedox Catalysis for Selective C(sp3 )-O Cleavages of Phosphinated Alcohols to Carbanions.

ABSTRACT: We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage of C(sp3 )-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(sp3 )-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.

SUBMITTER: Tian X 

PROVIDER: S-EPMC8518744 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

Json Xml
altmetric image

Publications

Electro-mediated PhotoRedox Catalysis for Selective C(sp<sup>3</sup> )-O Cleavages of Phosphinated Alcohols to Carbanions.

Tian Xianhai X   Karl Tobias A TA   Reiter Sebastian S   Yakubov Shahboz S   de Vivie-Riedle Regina R   König Burkhard B   Barham Joshua P JP  

Angewandte Chemie (International ed. in English) 20210816 38

We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage of C(sp<sup>3</sup> )-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  ...[more]

Similar Datasets

Unknown Photoredox-mediated remote C(sp<sup>3</sup>)-H heteroarylation of free alcohols.
| S-EPMC6345347 | biostudies-literature
Unknown Site-selective remote C(sp<sup>3</sup>)-H heteroarylation of amides via organic photoredox catalysis.
| S-EPMC6800443 | biostudies-literature
Unknown Site-Selective, Remote sp<sup>3</sup> C-H Carboxylation Enabled by the Merger of Photoredox and Nickel Catalysis.
| S-EPMC6773098 | biostudies-literature
Unknown Photoredox Catalysis-Enabled Sulfination of Alcohols and Bromides.
| S-EPMC10680125 | biostudies-literature
Unknown Decarboxylative sp<sup>3</sup> C-N coupling via dual copper and photoredox catalysis.
| S-EPMC6106865 | biostudies-literature
Unknown Site-selective coupling of remote C(sp<sup>3</sup>)-H/<i>meta</i>-C(sp<sup>2</sup>)-H bonds enabled by Ru/photoredox dual catalysis and mechanistic studies.
| S-EPMC9093131 | biostudies-literature
Unknown Asymmetric benzylic C(sp<sup>3</sup>)-H acylation via dual nickel and photoredox catalysis.
| S-EPMC8192574 | biostudies-literature
Unknown Room temperature C(sp<sup>2</sup>)-H oxidative chlorination <i>via</i> photoredox catalysis.
| S-EPMC5642143 | biostudies-literature
Unknown Modulating stereoselectivity in allylic C(sp<sup>3</sup>)-H bond arylations via nickel and photoredox catalysis.
| S-EPMC9892578 | biostudies-literature
Unknown Alcohols as Latent Coupling Fragments for Metallaphotoredox Catalysis: sp<sup>3</sup>-sp<sup>2</sup> Cross-Coupling of Oxalates with Aryl Halides.
| S-EPMC5464990 | biostudies-literature