Cationic Rhodium(I) Tetrafluoroborate Catalyzed Intramolecular Carbofluorination of Alkenes via Acyl Fluoride C-F Bond Activation

Tomoki Yoshida; Masaya Ohta; Tomoya Emmei; Takuya Kodama; Mamoru Tobisu

doi:10.1002/anie.202303657

Cationic Rhodium(I) Tetrafluoroborate Catalyzed Intramolecular Carbofluorination of Alkenes via Acyl Fluoride C-F Bond Activation

Angew Chem Int Ed Engl. 2023 Jun 5;62(23):e202303657. doi: 10.1002/anie.202303657. Epub 2023 Apr 26.

Authors

Tomoki Yoshida¹, Masaya Ohta¹, Tomoya Emmei¹, Takuya Kodama^{1

2}, Mamoru Tobisu^{1

2}

Affiliations

¹ Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka, 565-0871, Japan.
² Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka, 565-0871, Japan.

PMID: 37000460
DOI: 10.1002/anie.202303657

Abstract

The C-F bond of acyl fluorides can be cleaved and added across tethered alkenes in the presence of a cationic rhodium(I) tetrafluoroborate catalyst. This 1,2-carbofluorination reaction offers a powerful method for the synthesis of tertiary alkyl fluoride derivatives with an atom economy of 100 %. Mechanistic studies indicate that the concerted action of a rhodium cation and a tetrafluoroborate anion is key for the success of this catalytic cleavage and formation of C-F bonds in a controlled manner.

Keywords: Acyl Fluorides; C−F Bond Activation; Fluorination; Insertion; Rhodium Catalysis.

Grants and funding

JP21H04682/Japan Society for the Promotion of Science