Fluorinative α-cleavage of cyclic ketoximes with diethylaminosulfur trifluoride: an efficient synthesis of fluorinated carbonitriles

Kirihara, Masayuki; Niimi, Kanako; Momose, Takefumi

doi:10.1039/a607749h

Cited by 17 publications

(8 citation statements)

References 10 publications

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“…B. 142 und 144 ) hervorruft, wobei das kationische Intermediat durch Fluorid abgefangen wird (Schema ) 99. Diese Reaktion wird von Substraten bevorzugt, die elektronenschiebende Substituenten in α‐Position zu dem Oximinokohlenstoffatom tragen.…”

Section: Fortschritt Und Anwendungenunclassified

C‐C‐Fragmentierung: Herkunft und jüngste Anwendungen

2013

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Sechzig Jahre sind vergangen, seit Eschenmoser und Frey den Archetyp der C‐C‐Fragmentierung beschrieben. Rasch folgten neue Fragmentierungen und mehrere Varianten des Originals. Viele dieser Variationen, einschließlich der Beckmann‐, Grob‐, Wharton‐, Marshall‐ und der Eschenmoser‐Tanabe‐Fragmentierungen, sowie weiteren, wurden im Laufe der Jahre in Übersichten besprochen, eine genaue Untersuchung des Ursprungs von Fragmentierungen steht aber noch aus. Vor kurzem tauchten neue nützliche Methoden auf, insbesondere Fragmentierungen, die zu Alkinen und Allenen führen, und solche Reaktionen wurden auf eine Reihe an komplexen Leitmotiven und Naturstoffe angewendet. Dieser Aufsatz verfolgt die Entwicklung der Fragmentierungen und bietet eine Zusammenfassung der Methoden, Anwendungen und neue Einblicke in heterolytische C‐C‐Fragmentierungen der letzten zwanzig Jahre.

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Section: Fortschritt Und Anwendungenunclassified

C‐C‐Fragmentierung: Herkunft und jüngste Anwendungen

2013

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“…14 (G) Kirihara et al showed that cyclic ketoximes reacted with DAST affording fluorinated carbonitriles in good yields. 15 (H) DAST is a nucleophilic fluorination reagent but under appropriate conditions it can also serve as a catalyst. For instance, Lafarge et al reported that DAST can induce intramolecular cyclization of (1,2)-amido-alcohols to 2-oxazolines.…”

Section: Abstractsmentioning

confidence: 99%

Diethylaminosulfur Trifluoride (DAST)

Ferreira¹

2006

Synlett

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This feature focuses on a reagent chosen by a postgraduate, highlighting the uses and preparation of the reagent in current research Diethylaminosulfur Trifluoride (DAST)Compiled by Sabrina Baptista Ferreira Sabrina Baptista Ferreira was born in Rio de Janeiro, Brazil in 1979. She received her Industrial Pharmacy degree from Universidade Federal Fluminense in 2001 and her MSc in Chemistry from Universidade Federal do Rio de Janeiro in 2004. She is currently working toward her PhD under supervision of Prof. Vitor F. Ferreira (Universidade Federal Fluminese) and Prof. Carlos Roland Kaiser (Universidade Federal do Rio de Janeiro). Her research interests focus on the synthesis of diazo compounds, nucleosides, fluoro compounds and carbohydrates.

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“…This study was inspired by two seminal works of Momose and Shibata: (1) In 1997, Momose disclosed the fluorinative C–C bond cleavage of α,α-diakyl-substituted cyclic oximes using DAST as a bifunctional fluoride source . In this work, oxime activation by an electrophilic trifluorosulfur was followed by fluoride addition at the α-carbon of the oxime; this concerted reaction constructed a fluorinated quaternary carbon center instead of yielding a general Beckmann rearrangement product.…”

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confidence: 99%

“…On the basis of the prior mechanistic proposals of fluoride-mediated reactions, , a plausible reaction mechanism was proposed (Scheme a). The oxime activation is initiated by the electrophilic trifluorosulfur moiety of DAST, which releases HF.…”

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confidence: 99%

Synthesis of Acyl Fluorides via DAST-Mediated Fluorinative C–C Bond Cleavage of Activated Ketones

Kim

Lim

2020

Org. Lett.

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A new protocol for preparation of acyl fluorides was developed by recognizing activated ketones as starting materials. The method provides a different scope compared with previously reported methods that employ carboxylic acids as substrates. A working hypothesis of pull-and-push-driven fluorinative C–C bond cleavage was successfully demonstrated by the simple addition of diethylaminosulfur trifluoride (DAST) derivatives to α-oximinoketones. The designed reaction system led to a highly efficient and chemoselective reaction. The wide availability of the ketones allowed for a range of synthetically useful aryloyl and aliphatic acyl fluorides including those containing chiral skeletons. The method is mild, fast, scalable, and potentially one-pot operative.

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Fluorinative α-cleavage of cyclic ketoximes with diethylaminosulfur trifluoride: an efficient synthesis of fluorinated carbonitriles

Cited by 17 publications

References 10 publications

C‐C‐Fragmentierung: Herkunft und jüngste Anwendungen

C‐C‐Fragmentierung: Herkunft und jüngste Anwendungen

Diethylaminosulfur Trifluoride (DAST)

Synthesis of Acyl Fluorides via DAST-Mediated Fluorinative C–C Bond Cleavage of Activated Ketones

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