The Generation of Difluoroketenimine and Its Application in the Synthesis of α,α‐Difluoro‐β‐amino Amides

Zhang, Rui; Zhang, Zhikun; Zhou, Qi; Yu, Lefei; Wang, Jianbo

doi:10.1002/ange.201901591

Cited by 9 publications

(2 citation statements)

References 53 publications

(23 reference statements)

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“…[6] Among them, fluorinated ketenimines are understudied, most likely because only few synthetic methods are available to prepare them. As a matter of fact since the seminal work of Knunyants in 1965 on N ‐aryl‐bis(trifluoromethyl)ketenimines, [7] only the trifluoromethyl and bis(difluoro) derivatives by, respectively, Katagiri in 2009 [8] and Wang in 2019 [9] were reported (Scheme 1 B). The SCF 3 substituent has witnessed in recent years a huge interest and different methods for its direct introduction by means of electrophilic, nucleophilic as well as radical sources have been assessed [10] .…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Use of Trifluoromethylthiolated Ketenimines

Guérin

Pikun

Morioka

et al. 2020

Chemistry A European J

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The synthesis of trifluoromethylthiolated ketenimines is herein described. They are easily synthesized from the corresponding a-trifluoromethylthiolated oximes upon activationw ith triflic anhydride and ab ase. The presumed nitriliumi on resulting from the Beckmann rearrangement is deprotonated to lead to the key intermediate, whose stabilityb rought by the fluorinated substituent was unforeseeable. The reaction of these new building blocks with av ariety of nucleophiles affords av ast array of cyclic and acyclic productsb earing the valuable SCF 3 moiety.

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Section: Methodsmentioning

confidence: 99%

Synthesis and Use of Trifluoromethylthiolated Ketenimines

Guérin

Pikun

Morioka

et al. 2020

Chemistry A European J

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“…The transformation of difluorocarbene (:CF 2 ) has emerged as a powerful difluorination platform, which can be widely used to introduce fluorine into organic molecules. [1][2][3][4] Typical conversion of difluorocarbene, including attachment with a nucleophile and an electrophile, [5][6][7][8][9][10][11][12][13][14][15][16] Wittig reaction with carbonyls, [17][18][19][20] [2+1] cycloaddition with alkenes or alkynes 21 , metal-difluorocarbene involved catalytic coupling [22][23][24] and combining with other carbene, [25][26][27][28][29] can quickly construct different organofluorine compounds, such as gemdifluoroalkenes and gem-difluorocyclopropanes and other gem-difluorinated compounds (Fig. 1A).…”

Section: Introductionmentioning

confidence: 99%

Atom Recombination of Difluorocarbene Enables 3-Fluorinated Oxindoles from 2-Aminoarylketones

et al. 2022

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Contrary to the traditional implementation as a difluoromethyl group and recently disclosed role of C1 synthons in synthetic organic chemistry, difluorocarbene (:CF 2 ) is reported herein to proceed unprecedented atom recombination as both C1 synthon and F1 reagent simultaneously to render valuable 3-fluorinated oxindoles from 2aminoarylketones. The reaction does not require any catalyst and features a broad range of substrate scope with good functional group compatibility and ease of execution. This transformation could be employed to the quickconstructions of certain bioactive molecule derivatives. The mechanistic experiments and DFT calculations indicate that this atom recombination reaction of difluorocarbene for the synthesis of 3-fluorinated oxindoles may involve a rearrangement process of epoxide intermediates.

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Triazenyl Alkynes as Versatile Building Blocks in Multicomponent Reactions: Diastereoselective Synthesis of β‐Amino Amides

et al. 2021

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Multicomponent reactions (MCRs) are powerful tool for the construction of polyfunctional molecules in an operationally simple and atom-economic manner, and the discovery of novel MCRs requests various building blocks. Herein, triazenyl alkynes were disclosed as versatile building blocks in a multicomponent reaction with carboxylic acids, aldehydes and anilines to furnish b-amino amides with the achievement of high diastereoselectivity and structural diversity. In this process, triazenyl alkynes were bifunctional so that the alkyne moiety acts as C2 fragment and triazene serves as directing group to modulate the transition state thus achieving high diastereoselectivity, in consistence with DFT calculations. Furthermore, the triazenyl group also enables diverse late-stage transformation. This protocol opens a new vision for the discovery of building block and rational design of MCRs.

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The Generation of Difluoroketenimine and Its Application in the Synthesis of α,α‐Difluoro‐β‐amino Amides

Cited by 9 publications

References 53 publications

Synthesis and Use of Trifluoromethylthiolated Ketenimines

Synthesis and Use of Trifluoromethylthiolated Ketenimines

Atom Recombination of Difluorocarbene Enables 3-Fluorinated Oxindoles from 2-Aminoarylketones

Triazenyl Alkynes as Versatile Building Blocks in Multicomponent Reactions: Diastereoselective Synthesis of β‐Amino Amides

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