Direct trifluoroethylation of carbonyl sulfoxonium ylides using hypervalent iodine compounds

Radell Echemendía; Carlee A Montgomery; Fabio Cuzzucoli; Antonio C B Burtoloso; Graham K Murphy

doi:10.3762/bjoc.20.263

Direct trifluoroethylation of carbonyl sulfoxonium ylides using hypervalent iodine compounds

Beilstein J Org Chem. 2024 Dec 4:20:3182-3190. doi: 10.3762/bjoc.20.263. eCollection 2024.

Authors

Radell Echemendía^{1

2}, Carlee A Montgomery², Fabio Cuzzucoli², Antonio C B Burtoloso¹, Graham K Murphy²

Affiliations

¹ São Carlos Institute of Chemistry, University of São Paulo, 13560-970, São Carlos, SP, Brazil.
² Department of Chemistry, University of Waterloo, 200 University Ave W., Waterloo, Ontario, Canada.

Abstract

A novel study on the hypervalent iodine-mediated polyfluoroalkylation of sulfoxonium ylides was developed. Sulfoxonium ylides, known for their versatility and stability, are promising substrates for numerous transformations in synthetic chemistry. This report demonstrates the successful derivatization of sulfoxonium ylides with trifluoroethyl or tetrafluoropropyl groups, and provides valuable insights into the scope and limitations of this approach. Nineteen examples have been prepared (45-92% yields), with structural diversity modified at two key sites on the sulfoxonium ylide reactants. Finally, DFT calculations provided insights about the mechanism of this transformation, which strongly suggest that an S_N2 reaction is operative.

Keywords: DFT calculations; alkylation; fluorine chemistry; hypervalent iodine; sulfoxonium ylide; sulphur ylides.

Grants and funding

We would like to thank the São Paulo Research Foundation (FAPESP) for financial support (2023/02675-7) and in the form of fellowship grants to RE (2019/12300-5; 2022/09140-9). We also thank the Natural Sciences and Engineering Research Council (NSERC) of Canada for funding (DG 2019-04086, 2024-04404). FC acknowledges NSERC for a doctoral scholarship, and CAM acknowledges OGS and NSERC for graduate scholarships.