/ E-Alerts

Cobalt-catalyzed C–H cyanations: Insights into the reaction mechanism and the role of London dispersion

Eric Detmar, Valentin Müller, Daniel Zell, Lutz Ackermann and Martin Breugst

Beilstein J. Org. Chem. 2018, 14, 1537–1545. https://doi.org/10.3762/bjoc.14.130

Supporting Information

Supporting Information File 1: Cartesian coordinates, energies of all calculated structures, and details of computational methods.
Format: PDF	Size: 2.5 MB	Download

Cite the Following Article

Cobalt-catalyzed C–H cyanations: Insights into the reaction mechanism and the role of London dispersion

Eric Detmar, Valentin Müller, Daniel Zell, Lutz Ackermann and Martin Breugst

Beilstein J. Org. Chem. 2018, 14, 1537–1545. https://doi.org/10.3762/bjoc.14.130

How to Cite

Detmar, E.; Müller, V.; Zell, D.; Ackermann, L.; Breugst, M. Beilstein J. Org. Chem. 2018, 14, 1537–1545. doi:10.3762/bjoc.14.130

Download Citation

Citation data can be downloaded as file using the "Download" button or used for copy/paste from the text window below.
Citation data in RIS format can be imported by all major citation management software, including EndNote, ProCite, RefWorks, and Zotero.

File format:

RIS

BibTeX

Include:

Citation for the article above

Citation and complete reference list for the article above

Download

TY  - JOUR
A1  - Detmar, Eric
A1  - Müller, Valentin
A1  - Zell, Daniel
A1  - Ackermann, Lutz
A1  - Breugst, Martin
T1  - Cobalt-catalyzed C–H cyanations: Insights into the reaction mechanism and the role of London dispersion
JF  - Beilstein Journal of Organic Chemistry
PY  - 2018///
VL  - 14
SP  - 1537
EP  - 1545
SN  - 1860-5397
DO  - 10.3762/bjoc.14.130
PB  - Beilstein-Institut
JA  - Beilstein J. Org. Chem.
UR  - https://doi.org/10.3762/bjoc.14.130
KW  - catalysis
KW  - C–H activation
KW  - density functional theory
KW  - London dispersion
KW  - reaction mechanisms
N2  - Carboxylate-assisted cobalt(III)-catalyzed C–H cyanations are highly efficient processes for the synthesis of (hetero)aromatic nitriles. We have now analyzed the cyanation of differently substituted 2-phenylpyridines in detail computationally by density functional theory and also experimentally. Based on our investigations, we propose a plausible reaction mechanism for this transformation that is in line with the experimental observations. Additional calculations, including NCIPLOT, dispersion interaction densities, and local energy decomposition analysis, for the model cyanation of 2-phenylpyridine furthermore highlight that London dispersion is an important factor that enables this challenging C–H transformation. Nonbonding interactions between the Cp* ligand and aromatic and C–H-rich fragments of other ligands at the cobalt center significantly contribute to a stabilization of cobalt intermediates and transition states.
ER  -

Presentation Graphic

Picture with graphical abstract, title and authors for social media postings and presentations.
Format: PNG	Size: 196.7 KB	Download

Citations to This Article

Up to 20 of the most recent references are displayed here.

Scholarly Works

Atsumi, S.; Nosaka, C.; Onodera, T.; Adachi, H.; Watanabe, T.; Kawada, M.; Shibuya, M.; Park, S. I.; Kwon, H. J. Enhanced Anticancer Activity of 7MeERT over Ertredin: A Comparative Study on Cancer Cell Proliferation and NDUFA12 Binding. Biomolecules 2024, 14, 1197. doi:10.3390/biom14091197
Rummel, L.; Schreiner, P. R. Advances and Prospects in Understanding London Dispersion Interactions in Molecular Chemistry. Angewandte Chemie 2024, 136. doi:10.1002/ange.202316364
Rummel, L.; Schreiner, P. R. Advances and Prospects in Understanding London Dispersion Interactions in Molecular Chemistry. Angewandte Chemie (International ed. in English) 2024, 63, e202316364. doi:10.1002/anie.202316364
de Carvalho, R. L.; Diogo, E. B. T.; Homölle, S. L.; Dana, S.; da Silva Júnior, E. N.; Ackermann, L. The crucial role of silver(I)-salts as additives in C-H activation reactions: overall analysis of their versatility and applicability. Chemical Society reviews 2023, 52, 6359–6378. doi:10.1039/d3cs00328k
Yuan, B.; Oliveira, J. C. A.; Ackermann, L. Understanding and Describing London Dispersion Effects in Transition-Metal-Catalyzed C–H Activations. Synlett 2023, 34, 1098–1112. doi:10.1055/a-2060-3288
Rösel, S.; Schreiner, P. R. Computational Chemistry as a Conceptual Game Changer: Understanding the Role of London Dispersion in Hexaphenylethane Derivatives (Gomberg Systems). Israel Journal of Chemistry 2022, 62. doi:10.1002/ijch.202200002
Gonzalez-Gomez, J. C.; Alonso, F. Organic Reaction Mechanisms Series; Wiley, 2021; pp 513–551. doi:10.1002/9781119531975.ch13
Ikawa, T.; Yamamoto, Y.; Heguri, A.; Fukumoto, Y.; Murakami, T.; Takagi, A.; Masuda, Y.; Yahata, K.; Aoyama, H.; Shigeta, Y.; Tokiwa, H.; Akai, S. Could London Dispersion Force Control Regioselective (2 + 2) Cyclodimerizations of Benzynes? YES: Application to the Synthesis of Helical Biphenylenes. Journal of the American Chemical Society 2021, 143, 10853–10859. doi:10.1021/jacs.1c05434
Pal, P.; Mondal, S.; Chatterjee, A.; Saha, R.; Chakrabarty, K.; Das, G. K. Revisited the mechanism of cobalt(III) catalyzed cyanation of arenes and heteroarenes: A DFT study. Computational and Theoretical Chemistry 2021, 1201, 113289. doi:10.1016/j.comptc.2021.113289
Aniban, X.; Hartwig, B.; Wuttke, A.; Mata, R. A. Dispersion forces in chirality recognition – a density functional and wave function theory study of diols. Physical chemistry chemical physics : PCCP 2021, 23, 12093–12104. doi:10.1039/d1cp01225h
Wu, F.; Deraedt, C.; Cornaton, Y.; Contreras-García, J.; Boucher, M.; Karmazin, L.; Bailly, C.; Djukic, J.-P. Making Base-Assisted C–H Bond Activation by Cp*Co(III) Effective: A NoncovalentInteraction-Inclusive Theoretical Insight and Experimental Validation. Organometallics 2020, 39, 2609–2629. doi:10.1021/acs.organomet.0c00253
Giese, M.; Albrecht, M. Alkyl-Alkyl Interactions in the Periphery of Supramolecular Entities: From the Evaluation of Weak Forces to Applications. ChemPlusChem 2020, 85, 715–724. doi:10.1002/cplu.202000077
Schlottmann, M.; Van Craen, D.; Baums, J.; Funes-Ardoiz, I.; Wiederhold, C.; Oppel, I. M.; Albrecht, M. Stability of Hierarchically Formed Titanium(IV) Tris(catecholate ester) Helicates with Cyclohexyl Substituents in DMSO. Inorganic chemistry 2020, 59, 1758–1762. doi:10.1021/acs.inorgchem.9b02988
Holtrop, F.; Visscher, K. W.; Jupp, A. R.; Slootweg, J. C. Steric attraction: A force to be reckoned with. Advances in Physical Organic Chemistry; Elsevier, 2020; Vol. 54, pp 119–141. doi:10.1016/bs.apoc.2020.08.001
Strauss, M. A.; Wegner, H. A. Evaluierung von London‐Dispersions‐ und Lösungsmittel‐Interaktionen an Alkyl‐Alkyl‐Grenzflächen mittels Azobenzolschaltern. Angewandte Chemie 2019, 131, 18724–18729. doi:10.1002/ange.201910734
Strauss, M. A.; Wegner, H. A. Exploring London Dispersion and Solvent Interactions at Alkyl-Alkyl Interfaces Using Azobenzene Switches. Angewandte Chemie (International ed. in English) 2019, 58, 18552–18556. doi:10.1002/anie.201910734
Uchida, K.; Togo, H. Transformation of aromatic bromides into aromatic nitriles with n-BuLi, pivalonitrile, and iodine under metal cyanide-free conditions. Tetrahedron 2019, 75, 130550. doi:10.1016/j.tet.2019.130550
Lu, Q.; Neese, F.; Bistoni, G. London dispersion effects in the coordination and activation of alkanes in σ-complexes: a local energy decomposition study. Physical chemistry chemical physics : PCCP 2019, 21, 11569–11577. doi:10.1039/c9cp01309a

Explore citations to this article at

Back To Article

Other Beilstein-Institut Open Science Activities

aromatic	the word “aromatic”
aromatic aldehyde	the word “aromatic” OR “aldehyde”
+aromatic +aldehyde	both words “aromatic” AND “aldehyde”
+aromatic -aldehyde	the word “aromatic” but NOT “aldehyde”
“aromatic aldehyde”	the exact phrase “aromatic aldehyde”
benz*	words which begin with “benz”, such as “benzene” or “benzyl”
benz*yl	words that begin with “benz” and end with “yl”, such as “benzyl” or “benzoyl”
benzyl~	words that are close to the word “benzyl”, such as “benzoyl” (i.e., fuzzy search)