Hydrosilane-Mediated Electrochemical Reduction of Amides

Okamoto, Kazuhiro; Nagahara, Shingo; Imada, Yasushi; Narita, Risako; Kitano, Yoshikazu; Chiba, Kazuhiro

doi:10.1021/acs.joc.1c00931

Cited by 11 publications

(10 citation statements)

References 42 publications

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“…Electrochemical conversion of silanes to silanones via a HAT reaction and subsequent oxidation to the silyl cation with consecutive reduction of an amide to an amine as suggested by Chiba and co-workers (top), reaction equation and conditions (bottom, BBD = boron-doped diamond). [170] Scheme 34. Electrochemical HAT mediated oxidation of hydrosilanes to silanols as suggested by Zhang and co-workers (top), reaction equation, conditions, and yield range of some relevant representatives of the electrochemical conversion (bottom, RVC = reticulated vitreous carbon).…”

Section: Discussionmentioning

confidence: 99%

“…In reference to the reductive synthesis of the Si − O bond to silanones, an oxidative approach is known. Via the hydrosilane mediated electrochemical reduction of amides to amines, the respective Si=O bond is formed as a consecutive reaction [170] . PhSiH 3 is converted to the silyl radical via a bromide mediator with a HAT reaction.…”

Section: Electrochemical Silane Synthesismentioning

confidence: 99%

Section: Electrochemical Silane Synthesismentioning

confidence: 99%

“…Via the hydrosilane mediated electrochemical reduction of amides to amines, the respective Si=O bond is formed as a consecutive reaction. [170] PhSiH 3 is converted to the silyl radical via a bromide mediator with a HAT reaction. In parallel, the reduction of the amide occurs, to generate the respective SiÀ C bond via recombination.…”

Section: Further Oxidative Si Bond Formationsmentioning

confidence: 99%

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General Concepts and Recent Advances in the Electrochemical Transformation of Chloro‐ and Hydrosilanes

2023

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Organosilanes play an important role in organic synthesis as well as in a variety of further areas, ranging from life science to transportation. Especially, the electrochemical access has become increasingly important in the past years and developed into an essential topic due to new conceptual approaches and mediated reaction control. With the commercial availability of high‐quality electrochemical equipment, the technical requirements for electro‐conversion are at hand to a wide audience. This results in the need for a concise survey of electrochemical silane transformation, appropriate for novices as well as experts alike. This review provides an overview of the most relevant work in this field, identifies common obstacles in working with chlorosilanes and hydrosilanes and bridges the gap between known techniques and novel methods with respect to their electrochemical conversion. The historical development is outlined with reference to the various cathodic as well as anodic conversions and should encourage to expand the research field of electrochemical silane transformation.

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Section: Discussionmentioning

confidence: 99%

Section: Electrochemical Silane Synthesismentioning

confidence: 99%

Section: Electrochemical Silane Synthesismentioning

confidence: 99%

Section: Further Oxidative Si Bond Formationsmentioning

confidence: 99%

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General Concepts and Recent Advances in the Electrochemical Transformation of Chloro‐ and Hydrosilanes

2023

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“…In 2021, the Chiba group reported a hydrosilane-mediated electroreduction of amides under mild reaction conditions (Scheme 37). 70 The reaction is initiated by the cathodic reduction of amide 192 to form radical anion species 194 , followed by SET to generate ketyl radical 195 . Upon trapping by the in situ produced Lewis acid ZnBr 2 , the iminium cation intermediate 196 is reduced by phenylsilane to afford hemiaminal 198 .…”

Section: Electroreduction Of Oxygenated Compoundsmentioning

confidence: 99%

A guide to organic electroreduction using sacrificial anodes

Wen

Guo

2023

Chem. Soc. Rev.

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Photoredox‐Catalyzed [3+2] annulation of Aromatic Amides with Olefins via Iminium Intermediates

Tang,

Yao,

et al. 2024

Angewandte Chemie

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Despite the preliminary success of transition metal‐catalyzed [3+2] annulation of amides with olefins, the corresponding radical‐type [3+2] annulation remains a laborious challenge. Herein we report the first photoredox‐catalyzed radical‐type [3+2] annulation of aromatic amides with olefins. We established an approach to generate unprecedented iminium radicals by reducing the oxyiminium intermediates, formed in situ from corresponding amides with Tf2O, via photoredox catalysis. The [3+2] annulation was achieved via stepwise radical process, instead of forming linear products via other pathways as previously reported. This annulation protocol exhibits excellent functional group tolerance, and a diversity of substrates are united under the photoredox conditions, affording iminium products that can be in situ diversified into 1‐indanones, enamines and amines. Mechanistic investigations indicate reduction of the oxyiminium intermediate to the iminium radicals by excited‐state of the photocatalyst initiates the catalytic cycle.

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Hydrosilane-Mediated Electrochemical Reduction of Amides

Cited by 11 publications

References 42 publications

General Concepts and Recent Advances in the Electrochemical Transformation of Chloro‐ and Hydrosilanes

General Concepts and Recent Advances in the Electrochemical Transformation of Chloro‐ and Hydrosilanes

A guide to organic electroreduction using sacrificial anodes

Photoredox‐Catalyzed [3+2] annulation of Aromatic Amides with Olefins via Iminium Intermediates

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