Home > Research > Publications & Outputs > Selective ortho-C−H Activation in Arenes withou...

Research

Electronic data

  • Ortho_C_H_activation_manuscript_ja_2022_046215_revised_with_highlights

    Rights statement: 12m

    Accepted author manuscript, 619 KB, PDF document

    Embargo ends: 1/01/50

    Available under license: CC BY-NC: Creative Commons Attribution-NonCommercial 4.0 International License

Links

Text available via DOI:

View graph of relations

Selective ortho-C−H Activation in Arenes without Functional Groups

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Published

Standard

Selective ortho-C−H Activation in Arenes without Functional Groups. / Chan, Antony; Jakoobi, Martin; Wang, Chenxu et al.
In: Journal of the American Chemical Society, Vol. 144, No. 26, 06.07.2022, p. 11564–11568.

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Harvard

Chan, A, Jakoobi, M, Wang, C, O'Neill, R, Aydin, G, Halcovitch, N, Boulatov, R & Sergeev, A 2022, 'Selective ortho-C−H Activation in Arenes without Functional Groups', Journal of the American Chemical Society, vol. 144, no. 26, pp. 11564–11568. https://doi.org/10.1021/jacs.2c04621

APA

Chan, A., Jakoobi, M., Wang, C., O'Neill, R., Aydin, G., Halcovitch, N., Boulatov, R., & Sergeev, A. (2022). Selective ortho-C−H Activation in Arenes without Functional Groups. Journal of the American Chemical Society, 144(26), 11564–11568. https://doi.org/10.1021/jacs.2c04621

Vancouver

Chan A, Jakoobi M, Wang C, O'Neill R, Aydin G, Halcovitch N et al. Selective ortho-C−H Activation in Arenes without Functional Groups. Journal of the American Chemical Society. 2022 Jul 6;144(26):11564–11568. Epub 2022 Jun 21. doi: 10.1021/jacs.2c04621

Author

Chan, Antony ; Jakoobi, Martin ; Wang, Chenxu et al. / Selective ortho-C−H Activation in Arenes without Functional Groups. In: Journal of the American Chemical Society. 2022 ; Vol. 144, No. 26. pp. 11564–11568.

Bibtex

@article{206aa32b843b4efe8c2fd6d4305bce8e,
title = "Selective ortho-C−H Activation in Arenes without Functional Groups",
abstract = "Aromatic C-H activation in alkylarenes is a key step for the synthesis of functionalised organic molecules from simple hydrocarbon precursors. Known examples of such C-H activations often yield mixtures of products resulting from activation of least-hindered C-H bonds. Here we report highly selective ortho-C-H activation in alkylarenes by simple iridium complexes. We demon-strate that the capacity of the alkyl substituent to override the typical preference of metal-mediated C-H activation for least hindered aromatic C-H bonds results from transient insertion of iridium into the benzylic C-H bond. This enables fast iridium insertion into the ortho-C-H bond, followed by regeneration of the benzylic C-H bond by reductive elimination. Bulkier alkyl substituents increase ortho-selectivity. The described chemistry comprises a conceptually new alternative to existing approaches to aromatic C-H bond activation.",
author = "Antony Chan and Martin Jakoobi and Chenxu Wang and Robert O'Neill and Gulsevim Aydin and Nathan Halcovitch and Roman Boulatov and Alexey Sergeev",
year = "2022",
month = jul,
day = "6",
doi = "10.1021/jacs.2c04621",
language = "English",
volume = "144",
pages = "11564–11568",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "AMER CHEMICAL SOC",
number = "26",

}

RIS

TY - JOUR

T1 - Selective ortho-C−H Activation in Arenes without Functional Groups

AU - Chan, Antony

AU - Jakoobi, Martin

AU - Wang, Chenxu

AU - O'Neill, Robert

AU - Aydin, Gulsevim

AU - Halcovitch, Nathan

AU - Boulatov, Roman

AU - Sergeev, Alexey

PY - 2022/7/6

Y1 - 2022/7/6

N2 - Aromatic C-H activation in alkylarenes is a key step for the synthesis of functionalised organic molecules from simple hydrocarbon precursors. Known examples of such C-H activations often yield mixtures of products resulting from activation of least-hindered C-H bonds. Here we report highly selective ortho-C-H activation in alkylarenes by simple iridium complexes. We demon-strate that the capacity of the alkyl substituent to override the typical preference of metal-mediated C-H activation for least hindered aromatic C-H bonds results from transient insertion of iridium into the benzylic C-H bond. This enables fast iridium insertion into the ortho-C-H bond, followed by regeneration of the benzylic C-H bond by reductive elimination. Bulkier alkyl substituents increase ortho-selectivity. The described chemistry comprises a conceptually new alternative to existing approaches to aromatic C-H bond activation.

AB - Aromatic C-H activation in alkylarenes is a key step for the synthesis of functionalised organic molecules from simple hydrocarbon precursors. Known examples of such C-H activations often yield mixtures of products resulting from activation of least-hindered C-H bonds. Here we report highly selective ortho-C-H activation in alkylarenes by simple iridium complexes. We demon-strate that the capacity of the alkyl substituent to override the typical preference of metal-mediated C-H activation for least hindered aromatic C-H bonds results from transient insertion of iridium into the benzylic C-H bond. This enables fast iridium insertion into the ortho-C-H bond, followed by regeneration of the benzylic C-H bond by reductive elimination. Bulkier alkyl substituents increase ortho-selectivity. The described chemistry comprises a conceptually new alternative to existing approaches to aromatic C-H bond activation.

U2 - 10.1021/jacs.2c04621

DO - 10.1021/jacs.2c04621

M3 - Journal article

VL - 144

SP - 11564

EP - 11568

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 26

ER -