Synthesis and Reactivity of α-Cumyl Bromodifluoromethanesulfenate: Application to the Radiosynthesis of [18 F]ArylSCF3

Jiang Wu; Qunchao Zhao; Thomas C Wilson; Stefan Verhoog; Long Lu; Véronique Gouverneur; Qilong Shen

doi:10.1002/anie.201813708

Synthesis and Reactivity of α-Cumyl Bromodifluoromethanesulfenate: Application to the Radiosynthesis of [¹⁸ F]ArylSCF₃

Angew Chem Int Ed Engl. 2019 Feb 18;58(8):2413-2417. doi: 10.1002/anie.201813708. Epub 2019 Jan 25.

Authors

Jiang Wu¹, Qunchao Zhao¹, Thomas C Wilson², Stefan Verhoog², Long Lu³, Véronique Gouverneur², Qilong Shen¹

Affiliations

¹ Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
² University of Oxford, Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, UK.
³ Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. China.

PMID: 30575245
DOI: 10.1002/anie.201813708

Abstract

A highly reactive electrophilic bromodifluoromethylthiolating reagent, α-cumyl bromodifluoro-methanesulfenate 1, was prepared to allow for direct bromodifluoromethylthiolation of aryl boron reagents. This coupling reaction takes place under copper catalysis, and affords a large range of bromodifluoromethylthiolated arenes. These compounds are amenable to various transformations including halogen exchange with [¹⁸ F]KF/K₂₂₂ , a process giving access to [¹⁸ F]arylSCF₃ in two steps from the corresponding aryl boronic pinacol esters.

Keywords: PET; boron reagents; bromodifluoromethylthiolation; fluorine; radiolabeling.

Abstract

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