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Updated: Jul 29, 2025

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Published on: April 9, 2018
Enantioselective Sulfonium-Claisen Rearrangement with Cinnamyl Thioethers.
Jiwon Jang1, Youngjin Bae1, Seunghoon Shin1
1Department of Chemistry, Research Institute for Natural Sciences and Center for New Directions in Organic Synthesis (CNOS), Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul 04763, Korea.
Researchers developed a new method for synthesizing skipped 1,4-dienes using cinnamyl thioethers in a gold-catalyzed sulfonium-Claisen rearrangement. This breakthrough achieves high enantioselectivity and yield, enabling access to valuable chiral compounds.
Area of Science:
- Organic Chemistry
- Catalysis
- Synthetic Methodology
Background:
- The sulfonium-Claisen rearrangement, catalyzed by gold, offers excellent control in synthesizing skipped 1,4-dienes.
- Previous attempts to use cinnamyl thioethers in this rearrangement failed due to cinnamyl cation dissociation.
Purpose of the Study:
- To overcome the limitations of using cinnamyl thioethers in the sulfonium-Claisen rearrangement.
- To develop a highly enantioselective synthesis of skipped 1,4-dienes from cinnamyl thioethers.
- To explore the transformation of synthesized 1,4-dienes into valuable chiral chromanone and chromene derivatives.
Main Methods:
- Fine-tuning bisphosphine ligands for gold catalysis.
- Employing the sulfonium-Claisen rearrangement with cinnamyl thioether derivatives.
- Chiral chromatography for enantiomeric excess determination.
Main Results:
- Successfully engaged cinnamyl thioethers in the [3,3]-sigmatropic rearrangement.
- Achieved high enantioselectivity and good yields of the desired 1,4-dienes.
- Demonstrated the conversion of products into optically active 2-chromanones and 4H-chromenes.
Conclusions:
- Developed a novel, highly enantioselective sulfonium-Claisen rearrangement for cinnamyl thioethers.
- Established a versatile synthetic route to chiral skipped 1,4-dienes.
- Provided access to valuable chiral chromanone and chromene scaffolds.
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