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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.
Abstract:
Sulfonium-Claisen rearrangement leveraged by the gold-catalyzed formation of allyl sulfonium intermediates has enabled an exceptional level of regio- and enantiocontrol for the synthesis of skipped 1,4-dienes. However, the application of cinnamyl thioether derivatives to the sulfonium-Claisen rearrangement has been unsuccessful so far due to the extensive dissociation of the cinnamyl cation. By fine-tuning bisphosphine ligands, we were able to engage cinnamyl thioethers in the [3,3]-sigmatropic rearrangement, delivering the desired 1,4-dienes in a highly enantioselective manner and in good yields. The resulting products could be transformed into optically active 2-chromanones and 4H-chromenes having a vinyl moiety.
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