An Asymmetric Redox Arylation: Chirality Transfer from Sulfur to Carbon through a Sulfonium [3,3]‐Sigmatropic Rearrangement
作者: Dr. Dainis KaldreDr. Boris MaryasinDaniel KaiserOliver GajsekProf. Dr. Leticia GonzálezProf. Dr. Nuno Maulide
作者单位: 1Institute of Organic Chemistry University of Vienna Währinger Strasse 38 1090 Vienna Austria
2 Institute of Theoretical Chemistry University of Vienna Währinger Strasse 17 1090 Vienna Austria
刊名: Angewandte Chemie International Edition, 2017, Vol.56 (8), pp.2212-2215
来源数据库: Wiley Journal
DOI: 10.1002/anie.201610105
关键词: asymmetric synthesischirality transferrearrangementsulfoxidesynamides
原始语种摘要: Abstract(#br)A general, asymmetric redox arylation of ynamides and thioalkynes with chiral sulfoxides is reported. This is the first example of a general 1,4‐chirality transfer from sulfur to a carbon stereocenter through a sulfonium [3,3]‐sigmatropic rearrangement. This reaction delivers α‐arylated thioesters and amides under mild conditions in an atom‐economical manner. The products are formed in high yields with enantiomeric ratios up to 99.5:0.5. Quantum chemical calculations suggest a mechanism for the chirality transfer from sulfur to carbon and explain the experimentally observed correlation of the enantioselectivity with both the catalyst and the substrate.
全文获取路径: Wiley  (合作)
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