Substituent-Promoted Thio-Belluš-Claisen Rearrangement with Difluoroketene
Sheng Xi1, Hongrui Zhang1, Xiaolei Zhang1
1Technical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis (IAS), State Key Laboratory of Material-Oriented Chemical Engineering, School of Chemistry and Molecular Engineering, Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816, China.
Abstract:
The thio-Belluš-Claisen rearrangement with difluoroketene is reported herein. By resorting to fluoride-initiated desilylative β-elimination of difluorobromoacetylsilane, a new protocol that enables controlled release of the unstable difluoroketene and its efficient capture by allyl thioether for the ensuing rearrangement is successfully developed. The presence of an electron-withdrawing group on the internal alkene site of allyl thioether is proven to be vital for this reaction by promoting the rearrangement through charge stabilization in the transition state.
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