A Nitrilium-Type <i>N</i> -Heterocyclic Aryne

The first solution-phase synthesis and reactivity of a nitrilium-type <i>N</i>-hetaryne are described. The 1,2-azaborine-derived 1,6-BN-aryne <b>2</b> exhibits [4 + 2], [3 + 2], and [2 + 2] cycloadditions and electrophilic aromatic substitution (EAS) reactivity. The observed regio- and diastereoselectivities of the cycloaddition and EAS products are consistent with a polarized aryne/nitrilium species. The free 1,6-BN-aryne <b>2</b> was isolated and characterized under matrix isolation conditions. A Lewis structure description where the 1,6-BN-aryne <b>2</b> resonates between two limiting (ketenimine (dominant) vs nitrilium) forms is consistent with DFT calculations. New 1,2-azaborine structures that are functionalized at the C6- and N-positions, including highly strained derivatives that were previously not accessible, can now be accessed using 1,6-BN-aryne <b>2</b> as a versatile synthetic building block.

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Publication Details

Journal
Journal of the American Chemical Society
Published
2025-06-02
DOI
https://doi.org/10.1021/jacs.5c05146
Citations
1
Primary Topic
Cyclization and Aryne Chemistry
Type
article
Field-Weighted Citation Impact
0.94

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article

A Nitrilium-Type N -Heterocyclic Aryne

Hugues Preud’homme, Marisol Sarmiento Alvarado, Holger F. Bettinger, Christina Tönshoff et al.
1 citations
Journal of the American Chemical Society
Cyclization and Aryne Chemistry
0.94
article

A Nitrilium-Type N -Heterocyclic Aryne

Hugues Preud’homme, Marisol Sarmiento Alvarado, Holger F. Bettinger, Christina Tönshoff, Clovis Darrigan, Lauren My-Linh Tran, Shih‐Yuan Liu, Anna Chrostowska, Bo Li
article en
1 citations

Abstract

The first solution-phase synthesis and reactivity of a nitrilium-type <i>N</i>-hetaryne are described. The 1,2-azaborine-derived 1,6-BN-aryne <b>2</b> exhibits [4 + 2], [3 + 2], and [2 + 2] cycloadditions and electrophilic aromatic substitution (EAS) reactivity. The observed regio- and diastereoselectivities of the cycloaddition and EAS products are consistent with a polarized aryne/nitrilium species. The free 1,6-BN-aryne <b>2</b> was isolated and characterized under matrix isolation conditions. A Lewis structure description where the 1,6-BN-aryne <b>2</b> resonates between two limiting (ketenimine (dominant) vs nitrilium) forms is consistent with DFT calculations. New 1,2-azaborine structures that are functionalized at the C6- and N-positions, including highly strained derivatives that were previously not accessible, can now be accessed using 1,6-BN-aryne <b>2</b> as a versatile synthetic building block.

Journal of the American Chemical SocietyVol. 147(23)
Boston College (US), Merck & Co., Inc., Rahway, NJ, USA (United States) (US), Université de Pau et des Pays de l'Adour (FR), Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux (FR), University of Tübingen (DE)
Université de Pau et des Pays de l'Adour, National Institute of General Medical Sciences
Openalex Percentile: Top 25%
Cyclization and Aryne Chemistry
0.94
DOISourceOpenAlex
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A Nitrilium-Type <i>N</i> -Heterocyclic Aryne — Hugues Preud’homme, Marisol Sarmiento Alvarado, et al. · Journal of the American Chemical Society (2025) | TGRS Research Map | TGRS