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DFT Study of Unstrained Ketone C-C Bond Activation via Rhodium(I)-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions

submitted on 27.11.2019, 19:51 and posted on 04.12.2019, 12:49 by Dengmengfei Xiao, Lili Zhao, Diego Andrada
Unstrained cyclic ketones can participate in cooperative Suzuki-Miyaura cross-coupling type reaction using rhodium(I)-based catalyst via C-C bond activation. The regioselectivity indicates a trend where the most substituted side is activated and it is controlled by the beta-substituents. In this work, Density Functional Theory (DFT) calculations have been carried out to disclose the underlying mechanism in the reaction of a ketone series and arylboronate using ylidene as ancillary ligand and pyridine as co-catalysts. The computed energies suggest the reductive elimination step with the highest energy while the reductive elimination has the highest energy barrier. By the means of the Activation Strain Model (ASM) of chemical reactivity, it is found that the ketone strain energy released on the oxidative addition does not control the relativity of the OA reactivity, but indeed is the interaction energy between Rh(I) and C-C bond the ruling effect. The effect of the beta-substituents on regioselectivity has been additionally studied.


ERC StG (EU 805113)

National Natural Science Foundation of China (Grant No. 21703099, 21993044, 21828101)

Natural Science Foundation of Jiangsu Province for Youth (Grant No: BK20170964)

Nanjing Tech University (Grant No. 39837132 and 39837123)


Email Address of Submitting Author


Saarland University



ORCID For Submitting Author


Declaration of Conflict of Interest

The authors declare no competing financial interest.