Carbodicarbene-Stibenium Ion-Mediated Functionalization of C(sp3)−H and C(sp)−H Bonds

Thumbnail Image
Download
Name

Angew Chem Int Ed - 2024 - Warring - Carbodicarbene‐Stibenium Ion‐Mediated Functionalization of C sp3 H and C sp H Bonds.pdf

Size

3.06 MB

Format

Adobe PDF

Checksum (MD5)

61c4f01cb55034980ff5f26fe295968f

Thumbnail Image
Download
Name

Angew Chem Int Ed - 2025 - - Correction to Carbodicarbene‐Stibenium Ion‐Mediated Functionalization of C sp3 H and C sp .pdf

Description
Correction
Size

132.39 KB

Format

Adobe PDF

Checksum (MD5)

b31f8094abfb1c5c4ee37547afdfb45e

Author(s)
Warring, Levi
•
Westendorff, Karl S
•
Bennett, Marc T
•
Nam, Kijeong
•
Stewart, Brennan M
•
Dickie, Diane A
•
Paolucci, Christopher
•
Gunnoe, T Brent
•
Gilliard, Robert J
Date Issued
September 8, 2024
Journal
Angewandte Chemie International Edition
Publisher
Wiley
Citation
L. Warring, K. S. Westendorff, M. T. Bennett, K. Nam, B. M. Stewart, D. A. Dickie, C. Paolucci, T. B. Gunnoe, R. J. Gilliard Jr., Angew. Chem. Int. Ed.2025, 64, e202415070.
Version
Final published version
Abstract
Main-group element-mediated C−H activation remains experimentally challenging and the development of clear concepts and design principles has been limited by the increased reactivity of relevant complexes, especially for the heavier elements. Herein, we report that the stibenium ion [(pyCDC)Sb][NTf2]3 (1) (pyCDC=bis-pyridyl carbodicarbene; NTf2=bis(trifluoromethanesulfonyl)imide) reacts with acetonitrile in the presence of the base 2,6-di-tert-butylpyridine to enable C(sp3)−H bond breaking to generate the stiba-methylene nitrile complex [(pyCDC)Sb(CH2CN)][NTf2]2 (2). Kinetic analyses were performed to elucidate the rate dependence for all the substrates involved in the reaction. Computational studies suggest that C−H activation proceeds via a mechanism in which acetonitrile first coordinates to the Sb center through the nitrogen atom in a κ1 fashion, thereby weakening the C−H bond which can then be deprotonated by base in solution. Further, we show that 1 reacts with terminal alkynes in the presence of 2,6-di-tert-butylpyridine to enable C(sp)−H bond breaking to form stiba-alkynyl adducts of the type [(pyCDC)Sb(CCR)][NTf2]2 (3 a–f). Compound 1 shows excellent specificity for the activation of the terminal C(sp)−H bond even across alkynes with diverse functionality. The resulting stiba-methylene nitrile and stiba-alkynyl adducts react with elemental iodine (I2) to produce iodoacetonitrile and iodoalkynes, while regenerating an Sb trication.
Terms of Use
Creative Commons Attribution-NonCommercial
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1002/anie.202415070
PrivacyPermissionsAccessibilityContact us
Notify us about copyright concerns.