Synthetic Aspects of Intermolecular S<sub>N</sub>Ar Reactions

Terrier, François

doi:10.1002/9783527656141.ch4

Modern Nucleophilic Aromatic Substitution 2013

DOI: 10.1002/9783527656141.ch4

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Synthetic Aspects of Intermolecular S_NAr Reactions

François Terrier

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Cited by 4 publications

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“…Heteroaryl amines are prevalent in small-molecule therapeutics and are of particular interest in medicinal contexts due to their unique hydrogen-bonding properties and high aqueous solubility . These motifs are frequently synthesized via nucleophilic aromatic substitution and cross-coupling reactions, wherein C(sp 2 )–N bond formation occurs between a nucleophilic alkyl amine and an electrophilic haloarene . Conversely, C(sp 3 )–N bond formation using widely available heteroaryl amines remains underdeveloped.…”

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Photocatalytic Anti-Markovnikov Hydroamination of Alkenes with Primary Heteroaryl Amines

Geunes,

Meinhardt,

et al. 2023

J. Am. Chem. Soc.

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We report a light-driven method for the intermolecular anti-Markovnikov hydroamination of alkenes with primary heteroaryl amines. In this protocol, electron transfer between an amine substrate and an excited-state iridium photocatalyst affords an aminium radical cation (ARC) intermediate that undergoes C−N bond formation with a nucleophilic alkene. Integral to reaction success is the electronic character of the amine, wherein increasingly electron-deficient heteroaryl amines generate increasingly reactive ARCs. Counteranion-dependent reactivity is observed, and iridium triflate photocatalysts are employed in place of conventional iridium hexafluorophosphate complexes. This method exhibits broad functional group tolerance across 55 examples of N-alkylated products derived from pharmaceutically relevant heteroaryl amines.

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confidence: 99%

Photocatalytic Anti-Markovnikov Hydroamination of Alkenes with Primary Heteroaryl Amines

Geunes,

Meinhardt,

et al. 2023

J. Am. Chem. Soc.

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A Heteroarylamine Library: Indium‐Catalyzed Nucleophilic Aromatic Substitution of Alkoxyheteroarenes with Amines

et al. 2018

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Under indium Lewis acid catalysis, electron-rich five-membered heteroaryl electrophiles fused with/without a benzene ring were found to couple with amines to produce heteroarylamines with broad structural diversity. The heteroarylamine formation proceeds through the cleavage of a heteroarylÀOMe bond by the nucleophilic attack of the amine based on the nucleophilic aromatic substitution (S N Ar) reaction. In contrast to the corresponding traditional S N Ar amination, the present S N Ar-based heteroaryl amination can be performed without relying on both heteroaryl electrophiles with electron-withdrawing groups and nucleophilicity-enhanced metal amides. High compatibility towards the functional groups such as NO 2 , Br, I, CF 3 , CN, CO 2 Et, pyridyl, thiazolyl, C=C, and OH groups was observed, thus showing the practicality and reliability of this method. Mechanistic studies indicated that a carbonÀindium bond is likely to be formed on the heteroaryl ring during the process. Scheme 3. Indium-catalyzed S N Ar amination of 3,4-dimethoxythiophene with aniline.Scheme 4. Indium-catalyzed S N Ar amination of 3-bromo-4methoxythiophene with aniline.Scheme 5. Indium-catalyzed tandem S N Ar reaction of 2methoxythiophene with N-methyl-p-toluidine.

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Micelle-enabled clean and selective sulfonylation of polyfluoroarenes in water under mild conditions

et al. 2018

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Synthetic Aspects of Intermolecular S_NAr Reactions

Cited by 4 publications

References 257 publications

Photocatalytic Anti-Markovnikov Hydroamination of Alkenes with Primary Heteroaryl Amines

Photocatalytic Anti-Markovnikov Hydroamination of Alkenes with Primary Heteroaryl Amines

A Heteroarylamine Library: Indium‐Catalyzed Nucleophilic Aromatic Substitution of Alkoxyheteroarenes with Amines

Micelle-enabled clean and selective sulfonylation of polyfluoroarenes in water under mild conditions

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Synthetic Aspects of Intermolecular SNAr Reactions

Cited by 4 publications

References 257 publications

Photocatalytic Anti-Markovnikov Hydroamination of Alkenes with Primary Heteroaryl Amines

Photocatalytic Anti-Markovnikov Hydroamination of Alkenes with Primary Heteroaryl Amines

A Heteroarylamine Library: Indium‐Catalyzed Nucleophilic Aromatic Substitution of Alkoxyheteroarenes with Amines

Micelle-enabled clean and selective sulfonylation of polyfluoroarenes in water under mild conditions

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Product

Resources

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Synthetic Aspects of Intermolecular S_NAr Reactions