Electrochemically driven regioselective C−H phosphorylation of group 8 metallocenes

Zheng, Hao; Liu, Changhui; Guo, Shiyu; He, Gu‐Cheng; Min, Xiang‐Ting; Zhou, Bo-Chao; Ji, Ding‐Wei; Hu, Yan‐Cheng

doi:10.1038/s41467-022-31178-7

Cited by 16 publications

(8 citation statements)

References 79 publications

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“…Proposed mechanism for ferrocene phosphorylation (Zheng et al, 2022). Frontiers in Chemistry frontiersin.org 13 was proved under the conditions of joint electrolysis of diphenylphosphine oxide and substituted acetylene at the oxidation potentials of the intermediate silver salt of diphenylphosphine oxide (10% of silver acetate was used as the catalyst), and this reaction affords benzo [b] phosphole derivatives (Scheme 19D) (Khrizanforova et al, 2018).…”

Section: Scheme 18mentioning

confidence: 99%

“…An example of autocatalysis was recently described in regioselective electrochemically driven C−H phosphorylation of metallocenes ( Zheng et al, 2022 ). The authors suggest that oxidized metallocene, an electrophile, is generated at the anode and reacts with the phosphoryl radical, the formation of the latter being promoted by the metallocene itself ( Scheme 17 ):…”

Section: Electrochemical Metal-free C–h Phosphorylation Of Aromatic H...mentioning

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 18mentioning

confidence: 99%

Section: Electrochemical Metal-free C–h Phosphorylation Of Aromatic H...mentioning

confidence: 99%

Recent advances in electrochemical C—H phosphorylation

et al. 2022

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“…45 Nevertheless, such a challenge has been greatly alleviated by the recent development of electrocatalysts. 46 Redox-active electrocatalysts can enable the generation of reaction intermediates at reduced potentials with improved chemo-, 47,48 regio-, 49,50 and stereo-selectivity. 51,52 Homogeneous electrocatalysts (sometimes referred as mediators) are often the first option for a variety of electroorganic reactions because of their high adaptability and selectivity.…”

Section: High-throughput Screening For Electrocatalystsmentioning

confidence: 99%

Accelerated Electrosynthesis Development Enabled by High-Throughput Experimentation

Chen

2023

Synthesis

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Electrochemical synthesis has recently emerged as an environmentally benign method for synthesizing value-added fine chemicals. Its unique reactivity has attracted significant interests of synthetic chemists to develop new redox chemistries. However, compared to conventional chemistry, the increased complexity caused by electrode materials, supporting electrolytes, and setup configurations create obstacles for efficient reaction discovery and optimization. The recent increasing adoption of high-throughput experimentation (HTE) in synthetic chemistry significantly expedites the synthesis development. Considering the potential of implementing HTE in electrosynthesis to tackle the challenges of increased parameter space, this short review aims at providing recent advances in the HTE technology for electrosynthesis, including electrocatalysts screening, device miniaturization, electroanalytical methods, artificial intelligence, and system integration. The discussed contents also cover some topics in HTE electrochemistry for areas other than synthetic chemistry, hoping to spark some inspirations for readers to use interdisciplinary techniques to solve challenges in synthetic electrochemistry.

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“…Among the reported synthetic methodologies, transition-metal-catalyzed direct phosphorylation of aryl C–H bonds is recognized as one of the most atom- and step-economical approaches (Scheme ). − However, a big obstacle to this approach is that phosphorus coupling partners, such as secondary phosphine oxides (SPOs) and H-phosphonates, normally have strong coordinating abilities and may induce expeditious deactivation of the metal catalysts. For instance, SPOs with phosphorus in a pentavalent state can equilibrate to trivalent phosphinous acids and act as P-donor ligands .…”

Section: Introductionmentioning

confidence: 99%

Well-Defined Rhodium Diphenylphosphine Oxide Complexes Relevant to Rh(III)-Catalyzed Aryl C–H Phosphorylation

Lin

et al. 2022

Organometallics

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Secondary phosphine oxides (SPOs) are often difficult coupling partners for transition-metal-catalyzed C–H phosphorylation reactions. Herein, a series of SPO-RhIII complexes relevant to RhIII-catalyzed C–H phosphorylation was isolated and fully characterized. Detailed research on their reactivities in C–H rhodation indicates the crucial role of a suitable base to reduce the deactivation of RhIII by SPOs. Finally, using silver carbonate as both a base and an oxidant, an efficient RhIII-catalyzed aryl C–H phosphorylation with diarylphosphine oxides was developed.

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Electrochemically driven regioselective C−H phosphorylation of group 8 metallocenes

Cited by 16 publications

References 79 publications

Recent advances in electrochemical C—H phosphorylation

Recent advances in electrochemical C—H phosphorylation

Accelerated Electrosynthesis Development Enabled by High-Throughput Experimentation

Well-Defined Rhodium Diphenylphosphine Oxide Complexes Relevant to Rh(III)-Catalyzed Aryl C–H Phosphorylation

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