Electrolytic partial fluorination of organic compounds 84

Zagipa, Bakenova; Hidaka, Asami; Cao, Yi

doi:10.1016/j.jfluchem.2005.12.006

Cited by 7 publications

(5 citation statements)

References 31 publications

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“…In the second half of the 2000s, the Fuchigami group reported several preparations of α‐monofluoro‐ and α,α‐difluoromethylene phosphonates by anodic fluorination of benzyl‐ and sulfenylmethylphosphonates [215–217] . This reaction is believed to proceed via oxidation at α‐position relative to the phosphonate group and subsequent nucleophilic fluorination of transient carbocations.…”

Section: Synthetic Methodsmentioning

confidence: 99%

Recent Advances in Synthesis of Difluoromethylene Phosphonates for Biological Applications

et al. 2021

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For almost 40 years, difluoromethylene phosphonates have proven to be versatile molecular tools in biochemical studies owing to their close resemblance to naturally occurring phosphates and phosphonates. As bioisosteric, non‐hydrolyzable analogs of these essential molecules, difluoromethylene phosphonates can target the critical parts of the cellular machinery and therefore exhibit a diverse spectrum of biological activity. In the past ten years, there have appeared many new methods for the synthesis of difluoromethylene phosphonates. Most notably, photoredox catalysis has firmly entered the field, while cross‐coupling and nucleophilic strategies have met considerable elaboration and refinement, entirely in accord with the current trends in synthetic organic chemistry. Herein, we introduce difluoromethylene phosphonates as a distinct, high‐tech subclass of synthetic phosphonates resulting from the research efforts on the cross‐section of organophosphorus, organofluorine, and bioorganic chemistry. We then proceed to the discussion of general methods for the preparation of difluoromethylene phosphonates, comprehensively reviewing reactions developed in the past 15 years while providing the context of earlier works where appropriate. Finally, we present selected examples of molecules with high biological activity, their biological targets, and the synthetic steps employed for their preparation.

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Section: Synthetic Methodsmentioning

confidence: 99%

Recent Advances in Synthesis of Difluoromethylene Phosphonates for Biological Applications

et al. 2021

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“…Next, we extended this anodic fluorination to a-(phenylthio)benzylphosphonate derivatives 3, 4 and diethyl [(phenylthio)(1-naphthyl)methyl]phosphonate (5). The electrolysis was carried out at a GC anode in Et 4 NF•3HF-MeNO 2 .…”

Section: Methodsmentioning

confidence: 99%

“…4 It is for these reasons that we thought to try an electrochemical approach to give fluorinated phosphonates. 5,6 Previously, we have successfully carried out the anodic fluorination of benzylphosphonate derivatives as shown in Scheme 1. 5 However, the anodic fluorination of an unsubstituted benzylphosphonate ester required an extremely large excess of electricity (28 F/mol) due to its high oxidation potential (E p ox : 2.39 V vs SSCE).…”

mentioning

confidence: 99%

Regioselective Anodic Fluorination of α-(Arylthio)benzylphosphonate Esters, α-(Arylthio)methylphosphonate Esters and Their Analogues

Hidaka¹,

Zagipa²,

Nagura³

2007

Synlett

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“…306,307 These seminal studies constitute the first examples of selective electrochemical fluorination of chalcogen compounds. Since then, a variety of distinct sulfide-based motifs, such as 2H-benzo [b][1,4]-thiazin-3(4H)-one (114j), 308 benzothiazole (114o), 309-311 2,3-dihydrothiochroman-4-one (114k), 312 1,3-dithiolan-4-one (114c), 313 lactam (114a), 308 1,3,4-oxadiazole (114l), 311,314 1,3-oxathiolan-5-one (114b), 315 pyrimidin-4(3H)-one (114h), 316 phosphonate (114d), 317,318 pyridine (114e), 310,319 pyrimidine (114g), 310,311,319,320 quinazolin-4(3H)-one (114i), 319 quinoline (114f), 310 1,3,4-thiadiazole (114m), 311,314 and 1,2,4-triazole (114n), 314 have been shown to be amenable to regioselective monofluorination (Scheme 29). Because of their good conductivity, non-flammability, non-volatility and thermal stability, ionic liquids, such as Et 3 NÁnHF, have found widespread use as solvents in electrochemical fluorination reactions.…”

Section: Anodic Halogenationmentioning

confidence: 99%

Electrochemical strategies for C–H functionalization and C–N bond formation

2018

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Conventional methods for carrying out carbon-hydrogen functionalization and carbon-nitrogen bond formation are typically conducted at elevated temperatures, and rely on expensive catalysts as well as the use of stoichiometric, and perhaps toxic, oxidants. In this regard, electrochemical synthesis has recently been recognized as a sustainable and scalable strategy for the construction of challenging carbon-carbon and carbon-heteroatom bonds. Here, electrosynthesis has proven to be an environmentally benign, highly effective and versatile platform for achieving a wide range of nonclassical bond disconnections via generation of radical intermediates under mild reaction conditions. This review provides an overview on the use of anodic electrochemical methods for expediting the development of carbon-hydrogen functionalization and carbon-nitrogen bond formation strategies. Emphasis is placed on methodology development and mechanistic insight and aims to provide inspiration for future synthetic applications in the field of electrosynthesis.

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Electrolytic partial fluorination of organic compounds 84

Cited by 7 publications

References 31 publications

Recent Advances in Synthesis of Difluoromethylene Phosphonates for Biological Applications

Recent Advances in Synthesis of Difluoromethylene Phosphonates for Biological Applications

Regioselective Anodic Fluorination of α-(Arylthio)benzylphosphonate Esters, α-(Arylthio)methylphosphonate Esters and Their Analogues

Electrochemical strategies for C–H functionalization and C–N bond formation

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