Electrochemical phosphorylation of arenes catalyzed by cobalt under oxidative and reductive conditions

Strekalova, Sofia; Grinenko, V. V.; Gryaznova, T. V.; Kononov, A. I.; Dolengovski, Egor L.; Budnikova, Yulia H.

doi:10.1080/10426507.2018.1540488

Cited by 7 publications

(5 citation statements)

References 28 publications

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“…Trialkyl phosphites bearing primary alkyl chains of different lengths reacted smoothly to give the corresponding phosphonate products (31)(32)(33)(34)(35)(36). The electrochemical method was also suitable for late-stage functionalization of relatively complex natural products and bioactive compounds (37)(38)(39)(40)(41)(42)(43)(44)(45)(46). Compounds that contained multiple aryl rings reacted at the most electron-rich one (38, 40, 41, and 46).…”

Section: Resultsmentioning

confidence: 99%

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Electrochemical C–H phosphorylation of arenes in continuous flow suitable for late-stage functionalization

et al. 2021

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The development of efficient and sustainable methods for carbon-phosphorus bond formation is of great importance due to the wide application of organophosphorus compounds in chemistry, material sciences and biology. Previous C–H phosphorylation reactions under nonelectrochemical or electrochemical conditions require directing groups, transition metal catalysts, or chemical oxidants and suffer from limited scope. Herein we disclose a catalyst- and external oxidant-free, electrochemical C–H phosphorylation reaction of arenes in continuous flow for the synthesis of aryl phosphorus compounds. The C–P bond is formed through the reaction of arenes with anodically generated P-radical cations, a class of reactive intermediates remained unexplored for synthesis despite intensive studies of P-radicals. The high reactivity of the P-radical cations coupled with the mild conditions of the electrosynthesis ensures not only efficient reactions of arenes of diverse electronic properties but also selective late-stage functionalization of complex natural products and bioactive compounds. The synthetic utility of the electrochemical method is further demonstrated by the continuous production of 55.0 grams of one of the phosphonate products.

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Section: Resultsmentioning

confidence: 99%

“…In this context, electrochemical C-H phosphorylation of electron-rich heteroaromatics 38,39 and arenes bearing directing groups 40,41 have been reported. Reactions of electrondeficient arenes require metal catalysts and impractical threeelectrode configuration in divided cells [42][43][44][45][46][47] .…”

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confidence: 99%

Electrochemical C–H phosphorylation of arenes in continuous flow suitable for late-stage functionalization

et al. 2021

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“…The development of efficient late-stage phosphorylation methods is of considerable importance, given that organophosphorus compounds have wide utilities in medicinal chemistry . The past few years have seen significant development of electrochemical phosphorylation methodologies. − In 2019, Budnikova and co-workers realized the metallaelectro-catalyzed coupling reactions of caffeine with dialkylphosphites (Scheme ). Interestingly, diverse transition metals, including Pd(OAc) 2 , AgOAc, and Bipy 3 Ni(BF 4 ) 2 proved to be efficient for these transformations, affording the phosphorylated caffeine in good yields of 62–80%.…”

Section: Elsf Of C–h Bondsmentioning

confidence: 99%

Electrochemical Late-Stage Functionalization

Wang,

Dana,

Long

et al. 2023

Chem. Rev.

112

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Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical or biological activities. LSF can thus greatly accelerate the development of medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical molecular synthesis has emerged as an environmentally friendly platform for the transformation of organic compounds. Over the past decade, electrochemical late-stage functionalization (eLSF) has gained major momentum, which is summarized herein up to February 2023.

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“…More recently, the same group achieved an elegant approach for the electrochemical phosphorylated aromatic compounds, [44] by using cobalt complex as a catalyst for the electrochemical oxidative or reductive reactions. Different diethyl phosphonates 25 and aryl derivatives 24 (scheme 17) could afford the desired products 26 with yield up to 80 % if the reaction was carried out in reductive condition and up to 68 % in oxidative condition.…”

Section: Electrochemically Induced Phosphorylation Reactionsmentioning

confidence: 99%

Electrochemical Phosphorylation of Organic Molecules

Sbei

Martins

Shirinfar

et al. 2020

The Chemical Record

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Organophosphorus chemistry is a broad field with multi-dimensional applications in research area of organic, biology, drug design and agrochemicals. Conventional methods have been adopted extensively to access phosphorylated compounds that rely on the use of toxic, moisture sensitive phosphorylating agents and occur in the presence of oxidants, catalysts, as well as high temperatures and harsh conditions are required for complete transformations. However, recent progress has been made for phosphorylation reactions using electricity to introduce green and sustainable synthetic procedures. These reactions can be performed at mild conditions and proceed with excellent atom economy. Herein, we targeted electrochemical phosphorylation reactions with generation of new bonds such as C(sp 3) À P, C(sp 2) À P, OÀ P, NÀ P, SÀ P and SeÀ P. This review is aimed to offer an overview of recent developments in the synthetic methodology to easy access of organophosphorus compounds using electrochemistry.

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Electrochemical phosphorylation of arenes catalyzed by cobalt under oxidative and reductive conditions

Cited by 7 publications

References 28 publications

Electrochemical C–H phosphorylation of arenes in continuous flow suitable for late-stage functionalization

Electrochemical C–H phosphorylation of arenes in continuous flow suitable for late-stage functionalization

Electrochemical Late-Stage Functionalization

Electrochemical Phosphorylation of Organic Molecules

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