These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
3 files

Computational Insights into Intramolecular Cross-Coupling of Quaternary Borate Salts

submitted on 16.02.2021, 08:42 and posted on 17.02.2021, 05:04 by Florian Matz, Arif Music, Dorian Didier, Thomas C. Jagau
Cross-coupling reactions for C-C bond formation represent a cornerstone of organic synthesis. In most cases, they make use of transition metals, which has several downsides. Recently, metal-free alternatives relying on electrochemistry have gained interest. One example of such a reaction is the oxidation of tetraorganoborate salts that initiates aryl-aryl and aryl-alkenyl couplings with promising selectivities. This work investigates the mechanism of this reaction computationally using density functional and coupled-cluster theory. Our calculations reveal a distinct difference between aryl-alkenyl and aryl-aryl couplings: While C-C bond formation occurs irreversibly and without an energy barrier if an alkenyl residue is involved, many intermediates can be identified in aryl-aryl couplings. In the latter case, intramolecular transitions between reaction paths leading to different products are possible. Based on the energy differences between these intermediates, we develop a kinetic model to estimate product distributions for aryl-aryl couplings.


Theoretical Chemistry of Unbound Electrons

European Research Council

Find out more...

DFG grant 2227/2-1

Fonds der Chemischen Industrie


Ludwig-Maximilians-Universität München

SFB 749:  Dynamics and Intermediates of Molecular Transformations

Deutsche Forschungsgemeinschaft

Find out more...


Email Address of Submitting Author


Catholic University of Leuven



ORCID For Submitting Author


Declaration of Conflict of Interest

There are no conflicts of interest to declare.