(CF <sub>3</sub> S) <sub>2</sub> C═S: Electrophilic Site at the Thiocarbonyl Sulfur for the Incorporation of Multiple CF <sub>3</sub> S Groups
Although the thiocarbonyl group is typically attacked at sulfur due to orbital control, strong σ-electron-withdrawing groups can invert this reactivity, rendering the carbon electrophilic. Herein, we demonstrate that (CF<sub>3</sub>S)<sub>2</sub>C═S, despite bearing two strongly electron-withdrawing CF<sub>3</sub>S groups, still exhibits electrophilicity primarily at the sulfur atom toward Grignard reagents. Strikingly, the stoichiometric ratio governs the pathway. Excess Grignard reagent affords sulfur addition products, whereas excess (CF<sub>3</sub>S)<sub>2</sub>C═S yields unprecedented tris(trifluoromethylthio)alkenes.
Authors
- Jin‐Hong Lin (ORCID: https://orcid.org/0000-0002-7000-9540)
- Jun Sun (ORCID: https://orcid.org/0000-0001-5411-0182)
- Mengqi Sun (ORCID: https://orcid.org/0000-0003-2475-4977)
- Ji-Chang Xiao
Institutions
- Shanghai University (CN)
- Shanghai Institute of Organic Chemistry (CN)
- Innovative Research (United States) (US)
- University of Chinese Academy of Sciences (CN)
- RE Hydrogen (United Kingdom) (GB)
Publication Details
- Journal
- Organic Letters
- Published
- 2025-12-25
- DOI
- https://doi.org/10.1021/acs.orglett.5c04874
- Citations
- 1
- Primary Topic
- Fluorine in Organic Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.79