Electro-mediated photoredox catalysis for selective C(sp3)–O cleavages of phosphinated alcohols to carbanions

Xianhai Tian; Tobias A. Karl; Sebastian Reiter; Shahboz Yakubov; Regina de Vivie-Riedle; Burkhard König; Joshua P. Barham

doi:10.1002/anie.202105895

Electro-mediated photoredox catalysis for selective C(sp³)–O cleavages of phosphinated alcohols to carbanions

Xianhai Tian, Tobias A. Karl, Sebastian Reiter, Shahboz Yakubov, Regina de Vivie-Riedle, Burkhard König^*, Joshua P. Barham^*

^*Corresponding author for this work

Pure And Applied Chemistry

Research output: Contribution to journal › Article › peer-review

117 Citations (Scopus)

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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.

Original language	English
Pages (from-to)	20817-20825
Number of pages	9
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	38
Early online date	24 Jun 2021
DOIs	https://doi.org/10.1002/anie.202105895
Publication status	Published - 13 Sept 2021

Funding

J.P.B. and X.T. thank the Alexander von Humboldt Foundation for funding, provided within the framework of the Sofja Kovalevskaja Award endowed by the German Federal Ministry of Education and Research. R.dV-R. and S.R. acknowledge funding by the German Research Foundation (DFG) under Germany's excellence strategy EXC 2089/1-390776260.

Keywords

deoxygenation
olefination
photoelectrochemistry
preassembly
radical anion

Access to Document

10.1002/anie.202105895Licence: CC BY 4.0

Tian-etal-ACIE-2021-Electro-mediated-PhotoRedox-catalysis-for-selective-Csp3-O-cleavagesFinal published version, 1.81 MBLicence: CC BY 4.0

Cite this

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title = "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.",

keywords = "deoxygenation, olefination, photoelectrochemistry, preassembly, radical anion",

author = "Xianhai Tian and Karl, \{Tobias A.\} and Sebastian Reiter and Shahboz Yakubov and \{de Vivie-Riedle\}, Regina and Burkhard K{\"o}nig and Barham, \{Joshua P.\}",

note = "Publisher Copyright: {\textcopyright} 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH",

year = "2021",

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T1 - Electro-mediated photoredox catalysis for selective C(sp3)–O cleavages of phosphinated alcohols to carbanions

AU - Tian, Xianhai

AU - Karl, Tobias A.

AU - Reiter, Sebastian

AU - Yakubov, Shahboz

AU - de Vivie-Riedle, Regina

AU - König, Burkhard

AU - Barham, Joshua P.

PY - 2021/9/13

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N2 - 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.

AB - 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.

KW - deoxygenation

KW - olefination

KW - photoelectrochemistry

KW - preassembly

KW - radical anion

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JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

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