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Aryl Silicon Nucleophiles in Bismuth Catalysis
Teresa Faber1, Sophia Engelhardt1, Josep Cornella1
1Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany.
Angewandte Chemie (International Ed. in English)
|February 10, 2025
Summary
This study introduces a novel bismuth-catalyzed method for synthesizing fluorinated thiosulfones using aryl silicon compounds. It demonstrates a unique catalytic cycle involving organometallic transformations and sulfur dioxide insertion.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Synthetic Organic Chemistry
Background:
- Aromatic fluorinated thiosulfones are valuable synthetic targets.
- Development of efficient catalytic methods for their synthesis remains a challenge.
- Aryl silicon nucleophiles offer a versatile platform for C-C and C-heteroatom bond formation.
Purpose of the Study:
- To develop a novel bismuth-catalyzed protocol for the synthesis of aromatic fluorinated thiosulfones.
- To explore the utility of aryl silicon nucleophiles in bismuth catalysis.
- To elucidate the mechanistic pathway of the catalytic cycle.
Main Methods:
- Bismuth-catalyzed cross-coupling reactions.
- Utilizing aryl silicates as silicon nucleophiles.
- Investigating organometallic intermediates and reaction mechanisms.
Main Results:
- A new catalytic protocol for aromatic fluorinated thiosulfone synthesis was established.
- Demonstrated the first use of aryl silicon nucleophiles in bismuth catalysis.
- Identified key organometallic transformations including transmetalation and SO2 insertion.
- Established a redox-neutral bismuth catalytic cycle.
Conclusions:
- The developed protocol offers an efficient route to aromatic fluorinated thiosulfones.
- Highlights the potential of aryl silicon compounds in bismuth-catalyzed reactions.
- Provides mechanistic insights into bismuth-mediated organometallic processes.
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