Nucleophilic difluoromethylation and difluoromethylenation of aldehydes and ketones using diethyl difluoromethylphosphonate

Beier, Petr; Alexandrova, Anastasia V.; Zibinsky, Mikhail; Prakash, G. K. Surya

doi:10.1016/j.tet.2008.10.006

Cited by 49 publications

(17 citation statements)

References 51 publications

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“…Since the C-F bond is one of the strongest bonds, C-F bond activation and cleavage is a field of current interest in organic chemistry [79], although less is known about the catalytic activation and cleavage methods. Photocatalytic reaction is one of the promising methods to promote the activation and cleavage of the C-F bond of fluorinated compounds under mild conditions.…”

Section: Defluorination Of Fluorinated Ap Derivativesmentioning

confidence: 99%

Reactivity of Trapped and Accumulated Electrons in Titanium Dioxide Photocatalysis

2017

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Electrons, photogenerated in conduction bands (CB) and trapped in electron trap defects (Ti ds ) in titanium dioxide (TiO 2 ), play crucial roles in characteristic reductive reactions. This review summarizes the recent progress in the research on electron transfer in photo-excited TiO 2 . Particularly, the reactivity of electrons accumulated in CB and trapped at Ti ds on TiO 2 is highlighted in the reduction of molecular oxygen and molecular nitrogen, and the hydrogenation and dehalogenation of organic substrates. Finally, the prospects for developing highly active TiO 2 photocatalysts are discussed.

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Section: Defluorination Of Fluorinated Ap Derivativesmentioning

confidence: 99%

Reactivity of Trapped and Accumulated Electrons in Titanium Dioxide Photocatalysis

2017

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“…13 The lipophilic hydrogen bonding capacity of the difluoromethyl group has led to its development as a bio-isostere of alcohols, 14 thiols 15 and hydroxamic acids. 16 Routes to access the difluoromethyl motif involve reaction of an aldehyde with sulfur tetrafluoride, 17 reaction of nucleophilic "RCF 2 -" species with electrophiles, [18][19][20][21] reaction of a nucleophilic C, S, N, or O nucleophiles with difluorocarbene, [22][23][24][25][26] or transfer of a difluoromethyl radical to an appropriate substrate. [27][28][29] To explore the enzymatic synthesis of a difluoromethyl group, an appropriate substrate was required.…”

Section: Methodsmentioning

confidence: 99%

Exploration of a potential difluoromethyl-nucleoside substrate with the fluorinase enzyme

Thompson

McMahon

Naismith

et al. 2016

Bioorganic Chemistry

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Exploration of a potential difluoromethyl-nucleoside substrate with the fluorinase enzyme, Bioorganic Chemistry (2015), doi: http:// dx.doi.org/10.1016/j.bioorg. 2015.11.003 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. AbstractThe investigation of a difluoromethyl-bearing nucleoside with the fluorinase enzyme is described. 5',5'-Difluoro-5'-deoxyadenosine 7 (F 2 DA) was synthesised from adenosine, and found to bind to the fluorinase enzyme by isothermal titration calorimetry with similar affinity compared to 5'-fluoro-5'-deoxyadenosine 2 (FDA), the natural product of the enzymatic reaction. F 2 DA 7 was found, however, not to undergo the enzyme catalysed reaction with L-selenomethionine, unlike FDA 2, which undergoes reaction with L-selenomethionine to generate Se-adenosylselenomethionine. A co-crystal structure of the fluorinase and F 2 DA 7 and tartrate was solved to 1.8 Å, and revealed that the difluoromethyl group bridges interactions known to be essential for activation of fluoride for reaction. An unusual hydrogen bonding interaction between the hydrogen of the difluoromethyl group and one of the hydroxyl oxygens of the tartrate ligand was also observed. The bridging interactions, coupled with the inherently stronger C-F bond in the difluoromethyl group, offers an explanation for why no reaction is observed.

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“…[241] Boronsäuren lassen sich mit Kupfer, Ethyldifluoriodacetat und N,N-Diethyldifluoriodacetamid difluormethylieren. [250] Auch Difluormethylphenylsulfoxid [251] und Difluormethylphosphonate [252] wurden als Reagentien eingesetzt. Nucleophile Methoden zur Difluormethylierung Nucleophile Synthesemethoden für a,a-Difluormethylenether sind zwar weiterhin in Gebrauch, ihre Bedeutung geht jedoch mit der Entwicklung milderer, effizienter elektrophiler Difluormethylierungen zurück.…”

Section: Elektrophile Difluormethylierung üBer Carbenzwischenstufenunclassified

Einführung von Fluor und fluorhaltigen funktionellen Gruppen

2013

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Die wichtigsten konzeptionellen Fortschritt auf dem Gebiet der Fluorierungen der letzten zehn Jahre wurden durch die Organo‐ und Übergangsmetallkatalyse ermöglicht. Die schwierigste Umwandlung ist weiterhin die Bildung der C‐F‐Stammbindung, was in erster Linie eine Folge der hohen Hydratationsenergie von Fluorid, starker Metall‐Fluor‐Bindungen und der hoch polarisierten Bindungen zu Fluor ist. Den meisten Fluorierungen fehlt es immer noch an Allgemeingültigkeit, Vorhersagbarkeit und Kosteneffizienz. Trotz der Einschränkungen sind fluorierte Verbindungen mit modernen Fluorierungsmethoden leichter zugänglich als je zuvor. Vor allem beginnen sich die modernen Methoden auf Forschungsgebiete auszuwirken, die keine großen Materialmengen benötigen, z. B. die Wirkstoffentwicklung und die Positronenemissionstomographie. Diese Entwicklungen werden in diesem Aufsatz zusammengefasst und vor dem Hintergrund konventioneller Fluorierungsmethoden diskutiert.

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Nucleophilic difluoromethylation and difluoromethylenation of aldehydes and ketones using diethyl difluoromethylphosphonate

Abstract: New methodology for difluoromethylation and difluoromethylenation of aldehydes and ketones based on nucleophilic fluorination using diethyl difluoromethylphosphonate (1) was developed.

Cited by 49 publications

References 51 publications

Reactivity of Trapped and Accumulated Electrons in Titanium Dioxide Photocatalysis

Reactivity of Trapped and Accumulated Electrons in Titanium Dioxide Photocatalysis

Exploration of a potential difluoromethyl-nucleoside substrate with the fluorinase enzyme

Einführung von Fluor und fluorhaltigen funktionellen Gruppen

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