Visible-Light-Triggered Monofluoromethylation of Alkenes by Strongly Reducing 1,4-Bis(diphenylamino)naphthalene Photoredox Catalysis

Noto, Naoki; Koike, Takashi; Akita, Munetaka

doi:10.1021/acscatal.9b00473

Cited by 80 publications

(47 citation statements)

References 50 publications

(27 reference statements)

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“…Aryl amines have been established as useful photoredox catalysts in some light-induced reactions 59 , 60 . We questioned whether adjusting structures of conjugated aryl amines would enable us find effective visible-light photocatalysts for deuterodehalogenation of organic chlorides.…”

Section: Resultsmentioning

confidence: 99%

Organophotocatalytic selective deuterodehalogenation of aryl or alkyl chlorides

Lin

et al. 2021

Nat Commun

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Development of practical deuteration reactions is highly valuable for organic synthesis, analytic chemistry and pharmaceutic chemistry. Deuterodehalogenation of organic chlorides tends to be an attractive strategy but remains a challenging task. We here develop a photocatalytic system consisting of an aryl-amine photocatalyst and a disulfide co-catalyst in the presence of sodium formate as an electron and hydrogen donor. Accordingly, many aryl chlorides, alkyl chlorides, and other halides are converted to deuterated products at room temperature in air (>90 examples, up to 99% D-incorporation). The mechanistic studies reveal that the aryl amine serves as reducing photoredox catalyst to initiate cleavage of the C-Cl bond, at the same time as energy transfer catalyst to induce homolysis of the disulfide for consequent deuterium transfer process. This economic and environmentally-friendly method can be used for site-selective D-labeling of a number of bioactive molecules and direct H/D exchange of some drug molecules.

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Section: Resultsmentioning

confidence: 99%

Organophotocatalytic selective deuterodehalogenation of aryl or alkyl chlorides

Lin

et al. 2021

Nat Commun

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“…Der Anwendungsbereich von 17 wurde von Akita et al. auf die C‐Fluormethylierung von Alkenen unter Verwendung stark reduzierender Photoredox‐Katalysatoren ausgeweitet . Trotz der zeitaufwendigen (3 Tage) Synthese von 17 und der nur mäßigen Ausbeute, ist ein wichtiger Vorteil dieses Reagenzes seine Stabilität.…”

Section: Reagenzien Für Die Direkte Monofluormethylierungunclassified

Reagenzien für die selektive Fluormethylierung: Herausforderungen der Organofluorchemie

Reichel

Karaghiosoff

2020

Angewandte Chemie

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Die Einführung einer CH2F‐Gruppe in organische Moleküle ist in den letzten Jahren zweifellos zu einem sehr wichtigen Forschungsgebiet geworden. Aufgrund der vorteilhaften Eigenschaften von Organofluorverbindungen – wie ihre metabolische Stabilität – ist der Einbau der CH2F‐Gruppe als bioisosterer Ersatz für verschiedene funktionelle Gruppen eine attraktive Strategie, um z. B. neue Medikamente zu entwickeln. Darüber hinaus findet die Monofluormethyleinheit auch in der Agrochemie, in der pharmazeutischen Chemie und in der Feinchemie einen breiten Einsatz. Aufgrund des menschengemachten Klimawandels und des wachsenden Bedarfs an umweltfreundlichen industriellen Prozessen sind Alternativen zu den häufig verwendeten Fluormethylierungsmitteln auf FCKW‐ und HFBKW‐Basis (CH2FCl und CH2FBr) dringend erforderlich und im Montrealer Protokoll auch gefordert. Dies hat in letzter Zeit viele Forscher dazu veranlasst, die Entwicklung umweltfreundlicher Fluormethylierungsmittel zu entwickeln. Dieser Kurzaufsatz umfasst sowohl die klassischen als auch die neue Generation von Fluormethylierungsmitteln. Es werden Reagenzien und deren Vorläuferverbindungen diskutiert, die sowohl direkt als auch indirekt über elektrophile und nukleophile als auch radikalische Wege reagieren.

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“…Various compounds were fluoromethylated at O, S, N, or P in good yields by using sulfoximine 17 . The range of applications of 17 was extended by Akita and co‐workers to the C‐fluoromethylation of alkenes by using strongly reducing photoredox catalysts . Despite the time‐consuming (3 days) synthesis of 17 and the only moderate yield, an important advantage of this reagent is its stability.…”

Section: Reagents For Direct Monofluoromethylationmentioning

confidence: 99%

Reagents for Selective Fluoromethylation: A Challenge in Organofluorine Chemistry

2020

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The introduction of a monofluoromethyl moiety has undoubtedly become a very important area of research in recent years. Owing to the beneficial properties of organofluorine compounds, such as their metabolic stability, the incorporation of the CH2F group as a bioisosteric substitute for various functional groups is an attractive strategy for the discovery of new pharmaceuticals. Furthermore, the monofluoromethyl unit is also widely used in agrochemistry, in pharmaceutical chemistry, and in fine chemicals. The problems associated with climate change and the growing need for environmentally friendly industrial processes mean that alternatives to the frequently used CFC and HFBC fluoromethylating agents (CH2FCl and CH2FBr) are urgently needed and also required by the Montreal Protocol. This has recently prompted many researchers to develop alternative fluoromethylation agents. This Minireview summarizes both the classical and new generation of fluoromethylating agents. Reagents that act via electrophilic, nucleophilic, and radical pathways are discussed, in addition to their precursors.

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Visible-Light-Triggered Monofluoromethylation of Alkenes by Strongly Reducing 1,4-Bis(diphenylamino)naphthalene Photoredox Catalysis

Cited by 80 publications

References 50 publications

Organophotocatalytic selective deuterodehalogenation of aryl or alkyl chlorides

Organophotocatalytic selective deuterodehalogenation of aryl or alkyl chlorides

Reagenzien für die selektive Fluormethylierung: Herausforderungen der Organofluorchemie

Reagents for Selective Fluoromethylation: A Challenge in Organofluorine Chemistry

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