Mechanism of electrophilic fluorination with Pd(IV): fluoride capture and subsequent oxidative fluoride transfer
- Mechanism of electrophilic fluorination with Pd(IV): fluoride capture and subsequent oxidative fluoride transfer
- Br; t, JR; Lee, E; Boursalian, GB; Ritter, T
- Date Issued
- The Royal Society of Chemistry
- Electrophilic fluorinating reagents derived from fluoride are desirable for the synthesis of F-18-labeled molecules for positron emission tomography (PET). Here, we study the mechanism by which a Pd(IV)complex captures fluoride and subsequently transfers it to nucleophiles. The intermediate Pd(IV)-F is formed with high rates even at the nano-to micromolar fluoride concentrations typical for radiosyntheses with F-18 due to fast formation of an outer-sphere complex between fluoride and Pd(IV). The subsequent fluorine transfer from the Pd(IV)-F complex is proposed to proceed through an unusual SET/fluoride transfer/SET mechanism. The findings detailed in this manuscript provide a theoretical foundation suitable for addressing a more general approach for electrophilic fluorination with high specific activity F-18 PET imaging.
- TRANSITION-METAL-COMPLEXES; C-H FLUORINATION; CATALYZED ALLYLIC FLUORINATION; NUCLEAR MAGNETIC-RESONANCE; LATE-STAGE FLUORINATION; RADICAL CATIONS; REDUCTIVE ELIMINATION; STILBENE DERIVATIVES; XENON DIFLUORIDE; NUCLEOPHILIC FLUORINATION
- Article Type
- CHEMICAL SCIENCE, vol. 5, no. 1, page. 169 - 179, 2014-01
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