Pd-Catalyzed Oxidative C−H Arylation of (Poly)fluoroarenes with Aryl Pinacol Boronates and Experimental and Theoretical Studies of its Reaction Mechanism
Corresponding Author
Yudha P. Budiman
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 45363 Sumedang, Indonesia
Search for more papers by this authorMiftahussurur Hamidi Putra
Institute of Theoretical Chemistry, Ulm University, 89081 Ulm, Germany
Search for more papers by this authorMuhammad R. Ramadhan
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 45363 Sumedang, Indonesia
Search for more papers by this authorRaiza Hannifah
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 45363 Sumedang, Indonesia
Search for more papers by this authorChristian Luz
Institute of Inorganic Chemistry and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
Search for more papers by this authorIlham Z. Ghafara
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 45363 Sumedang, Indonesia
Search for more papers by this authorRustaman Rustaman
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 45363 Sumedang, Indonesia
Search for more papers by this authorEngela E. Ernawati
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 45363 Sumedang, Indonesia
Search for more papers by this authorTri Mayanti
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 45363 Sumedang, Indonesia
Search for more papers by this authorAxel Groß
Institute of Theoretical Chemistry, Ulm University, 89081 Ulm, Germany
Helmholtz Institute Ulm (HIU), Electrochemical Energy Storage, 89069 Ulm, Germany
Search for more papers by this authorUdo Radius
Institute of Inorganic Chemistry and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
Search for more papers by this authorTodd B. Marder
Institute of Inorganic Chemistry and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
Search for more papers by this authorCorresponding Author
Yudha P. Budiman
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 45363 Sumedang, Indonesia
Search for more papers by this authorMiftahussurur Hamidi Putra
Institute of Theoretical Chemistry, Ulm University, 89081 Ulm, Germany
Search for more papers by this authorMuhammad R. Ramadhan
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 45363 Sumedang, Indonesia
Search for more papers by this authorRaiza Hannifah
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 45363 Sumedang, Indonesia
Search for more papers by this authorChristian Luz
Institute of Inorganic Chemistry and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
Search for more papers by this authorIlham Z. Ghafara
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 45363 Sumedang, Indonesia
Search for more papers by this authorRustaman Rustaman
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 45363 Sumedang, Indonesia
Search for more papers by this authorEngela E. Ernawati
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 45363 Sumedang, Indonesia
Search for more papers by this authorTri Mayanti
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 45363 Sumedang, Indonesia
Search for more papers by this authorAxel Groß
Institute of Theoretical Chemistry, Ulm University, 89081 Ulm, Germany
Helmholtz Institute Ulm (HIU), Electrochemical Energy Storage, 89069 Ulm, Germany
Search for more papers by this authorUdo Radius
Institute of Inorganic Chemistry and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
Search for more papers by this authorTodd B. Marder
Institute of Inorganic Chemistry and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
Search for more papers by this authorAbstract
We report the synergistic combination of Pd(OAc)2 and Ag2O for the oxidative C−H arylation of (poly)fluoroarenes with aryl pinacol boronates (Ar-Bpin) in DMF as the solvent. This procedure can be conducted easily in air, and without using additional ligands, to afford the fluorinated unsymmetrical biaryl products in up to 98 % yield. Experimental studies suggest that the formation of [PdL2(C6F5)2] in DMF as coordinating solvent does not take place under the reaction conditions as it is stable to reductive elimination and thus would deactivate the catalyst. Thus, the intermediate [Pd(DMF)2(ArF)(Ar)] must be formed selectively to give desired arylation products. DFT calculations predict a low barrier (5.87 kcal/mol) for the concerted metalation deprotonation (CMD) process between C6F5H and the Pd(II) species formed after transmetalation between the Pd(II)X2 complex and aryl-Bpin which forms a Pd-Arrich species. Thus a Pd(Arrich)(Arpoor) complex is generated selectively which undergoes reductive elimination to generate the unsymmetrical biaryl product.
Conflict of interests
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
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