Electrocatalytic C–H phosphorylation through nickel(III/IV/II) catalysis

Zhang, Shou‐Kun; Vecchio, Antonio Del; Kuniyil, Rositha; Messinis, Antonis M.; Lin, Zhipeng; Ackermann, Lutz

doi:10.1016/j.chempr.2021.04.009

Cited by 35 publications

(24 citation statements)

References 57 publications

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“…Oxidation-induced reductive elimination requires the organic base 1,1,3,3-tetramethylguanidine (TMG) to be successful. The protons released in this way are converted into molecular hydrogen at the SCHEME 28 Ni-catalysed heteroarene phosphorylation using (iPrO) 2 P(O)H as phosphorylating reagent (Zhang et al, 2021).…”

Section: Scheme 25mentioning

confidence: 99%

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Recent advances in electrochemical C—H phosphorylation

et al. 2022

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The activation of C–H bond, and its direct one-step functionalization, is one of the key synthetic methodologies that provides direct access to a variety of practically significant compounds. Particular attention is focused on modifications obtained at the final stages of the synthesis of complicated molecules, which requires high tolerance to the presence of existing functional groups. Phosphorus is an indispensable element of life, and phosphorus chemistry is now experiencing a renaissance due to new emerging applications in medicinal chemistry, materials chemistry (polymers, flame retardants, organic electronics, and photonics), agricultural chemistry (herbicides, insecticides), catalysis (ligands) and other important areas of science and technology. In this regard, the search for new, more selective, low-waste synthetic routes become relevant. In this context, electrosynthesis has proven to be an eco-efficient and convenient approach in many respects, where the reagents are replaced by electrodes, where the reactants are replaced by electrodes, and the applied potential the applied potential determines their “oxidizing or reducing ability”. An electrochemical approach to such processes is being developed rapidly and demonstrates some advantages over traditional classical methods of C-H phosphorylation. The main reasons for success are the exclusion of excess reagents from the reaction system: such as oxidants, reducing agents, and sometimes metal and/or other improvers, which challenge isolation, increase the wastes and reduce the yield due to frequent incompatibility with these functional groups. Ideal conditions include electron as a reactant (regulated by applied potential) and the by-products as hydrogen or hydrocarbon. The review summarizes and analyzes the achievements of electrochemical methods for the preparation of various phosphorus derivatives with carbon-phosphorus bonds, and collects data on the redox properties of the most commonly used phosphorus precursors. Electrochemically induced reactions both with and without catalyst metals, where competitive oxidation of precursors leads to either the activation of C-H bond or to the generation of phosphorus-centered radicals (radical cations) or metal high oxidation states will be examined. The review focuses on publications from the past 5 years.

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Section: Scheme 25mentioning

confidence: 99%

“…Frontiers in Chemistry frontiersin.org cathode (Zhang et al, 2021). However, the scheme does not take into account the fact that the iodide ion is oxidized first, and the role of the substituted triarylphosphine, which is also relatively easily oxidized, is not clear.…”

Section: Scheme 25mentioning

confidence: 99%

Recent advances in electrochemical C—H phosphorylation

et al. 2022

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“…Electro-organic synthesis has emerged as an increasingly powerful tool for molecular syntheses with electricity as an atom-economic redox reagent, avoiding the use of traditional chemical redox agents. [1,2] Particularly, the merger of electrocatalysis with organometallic chemistry has set the stage for arene ortho-CÀ H functionalizations, [3] with key contributions by the groups of Mei, [4] Kakiuchi, [5] Xu, [6] Lei [7] and Ackermann, [8] among others (Scheme 1a). [9] In contrast, while methods for distal CÀ H functionalization are in high demand, [10][11][12][13][14] the remote arene diversification by metallaelectro-catalyzed CÀ H functionalization has thus far proven to be elusive.…”

Section: Introductionmentioning

confidence: 99%

Distal Ruthenaelectro‐Catalyzed meta‐C−H Bromination with Aqueous HBr

Wang¹,

Simon²,

Chen

et al. 2022

Angew Chem Int Ed

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While electrochemical ortho-selective CÀ H activations are well established, distal CÀ H activations continue to be underdeveloped. In contrast, we herein describe the electrochemical meta-CÀ H functionalization. The remote CÀ H bromination was accomplished in an undivided cell by RuCl 3 •3 H 2 O with aqueous HBr. The electrohalogenation proceeded under exogenous ligand-and electrolyte-free conditions. Notably, pyrazolylarenes were meta-selectively brominated at the benzenoid moiety, rather than on the electron-rich pyrazole ring for the first time. Mechanistic studies were suggestive of an initial ruthenacycle formation, and a subsequent ligand-to-ligand hydrogen transfer (LLHT) process to liberate the brominated product.

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“…Die organische Elektrosynthese hat sich zu einem wichtigen Werkzeug für die molekulare Synthese entwickelt, welche Elektrizität als atomökonomisches Redox-Reagenz nutzt. [1,2] Besonders die Verbindung aus Elektrokatalyse und organometallischer Chemie haben den Weg für die ortho-selektive Funktionalisierungen von Arenen bereitet, [3] wichtige Beiträge wurden unter anderem von Mei, [4] Kakiuchi, [5] Xu, [6] Lei [7] und Ackermann, [8] sowie Weiteren geleistet (Schema 1a). [9] Im Gegensatz hierzu sind Methoden für die distale Funktionalisierung weiterhin unterrepräsentiert, [10][11][12][13][14] die metallaelektro-katalysierte Modifikation der meta-Position in Arenen ist sogar noch nie beschrieben worden.…”

Section: Introductionunclassified

Distale Ruthenaelektro‐katalysierte meta‐C−H‐Bromierung mit wässriger HBr

et al. 2022

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Während elektrochemische ortho‐selektive C−H‐Aktivierungen bereits etabliert sind, bleiben die distalen C−H‐Aktivierungen weiterhin unterrepräsentiert. Hiermit beschreiben wir eine meta‐C−H‐Aktivierung. Die Bromierung der abgelegenen C−H‐Bindung wurde in einer ungeteilten Zelle unter Verwendung von RuCl3⋅3 H2O und wässriger HBr realisiert. Die Elektrohalogenierung verläuft ohne die Zugabe eines zusätzlichen Liganden und unter elektrolytfreien Bedingungen. Bemerkenswerterweise wurden Pyrazolylarene zum ersten Mal meta‐selektiv am Benzoidfragment und nicht am elektronenreichen Pyrazolring funktionalisiert. Mechanistische Studien legen die Bildung eines Ruthenazyklus nahe mit nachfolgendem Ligand‐zu‐Ligand‐Wasserstoff‐Transfer (LLHT), welcher schließlich das bromierte Produkt bildet.

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Electrocatalytic C–H phosphorylation through nickel(III/IV/II) catalysis

Cited by 35 publications

References 57 publications

Recent advances in electrochemical C—H phosphorylation

Recent advances in electrochemical C—H phosphorylation

Distal Ruthenaelectro‐Catalyzed meta‐C−H Bromination with Aqueous HBr

Distale Ruthenaelektro‐katalysierte meta‐C−H‐Bromierung mit wässriger HBr

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